Novel internally plasticizing and crosslinkable monomers and applications thereof

ABSTRACT

Novel compounds derived from traditional semi- drying and non-drying oils featuring internally plasticizing and crosslinkable properties are disclosed and claimed. Preferred embodiments include acrylate or methacrylate esters of hydroxy long-chain olefinic compounds derived from castor oil or lesquerella oil. A process for the preparation of the novel compounds is also disclosed, which involves esterification reaction of ethylenically unsaturated carboxylic acids or its derivatives with substituted hydroxy long-chain olefinic compounds. These compounds are suitable for forming latices, which form films at low minimum film forming temperatures (MFT) ranging from −5 to 10° C. and cure to above ambient glass transition (T g ) polymers without the use of traditional organic cosolvents which contribute to environmental pollution via volatile organic compounds (VOCs) emissions. These latices are therefore useful in waterborne coatings, contact and pressure sensitive adhesives, and inks.

BACKGROUND OF THE INVENTION

[0001] 1. Field of the Invention

[0002] This invention relates to new compositions of matter whichcontain an ethylenically unsaturated carboxylic ester moiety, and arederived from traditional semi-drying and non-drying oils. Moreparticularly, though not exclusively, this invention relates both tonovel compositions of acrylate and methacrylate esters of a long-chainolefinic moiety derived from non-drying oils such as castor oil orlesquerella oil and to a process for making these compositions. Theinvention is also directed to novel waterbome latex compositions formedfrom these novel acrylate or methacrylate compositions having utility incoatings, adhesives and inks to improve and enhance the generalapplication and performance properties of these formulations.

[0003] 2. Description of the Prior Art

[0004] Recent Congressional enactments have forced coatingsmanufacturers to develop new coating formulations that contain low VOCsyet feature good performance properties. However, attempts at developingnew formulations that contain environmentally acceptable low VOCs haveonly resulted in formulations with poor performance characteristicswhich are also economically unattractive.

[0005] One problem encountered by the coatings manufacturers is thedevelopment of formulations containing low VOC-coalescing aids orplasticizers. For instance, emulsion polymers are currently formulatedwith coalescing aids or plasticizers in order to form films at and belowambient conditions yet dry to films of sufficient glass transitiontemperature (T_(g)) to perform adequately at and above room temperature.In general, the ability of emulsion polymers to form or coalesce intofilm is governed by the minimum film forming temperature (MFT) of thepolymer in question, which typically approximates T_(g) of that polymer.Thus, there is a dilemma, i.e., low MFT polymers are required in orderto exhibit coalescence, flow, and surface wetting properties. However,if the polymer remains soft and tacky, the coatings are not usable.Therefore, it is necessary to develop a technology in which coatingformulations contain suitable ingredients with an initial low MFT,followed upon application forms nontacky, durable, hard, and waterresistant surfaces having a T_(g) significantly above their MFT.

[0006] There are few references in literature which describe low MFTcoating compositions which cure to form high T_(g) films. One suchexample utilizes a terpolymer binder known as Vinamul 3692, which isused in solventless paints. The terpolymer is formed from ethylene,vinyl acetate, and acrylated ethylene vinyl acetate. Although thephysical properties of the paint films are generally good, the latexsynthesis involves the use of ethylene in high pressure reactors. Such amanufacturing protocol is not available to most latex manufacturers andis not cost effective.

[0007] There have been many other reports that disclose coatingscompositions that cure or dry at ambient conditions into durableproducts. For example, vinylic derivatives of auto-oxidizable dryingoils have been synthesized, which are formulated into crosslinkableemulsion compositions. However, these emulsion compositions stillrequired the use of VOCs for film formation and formulation into usablecoatings. Moreover, the polymers possessed other drawbacks, i.e., thefree radical polymerizations of vinyl monomers of high iodine numberoils are kinetically unfavorable and the products exhibit moderate tomarked incompatibility.

[0008] Various other coating compositions which cure under ambientconditions are known in the prior art. A few such examples involvecuring by a chemical reaction such as epoxide-carboxylic acid reaction,isocyanate-moisture reaction, polyaziridine-carboxylic acid reaction,and activated methylene-unsaturated acrylic reaction.

[0009] There are also literature references which disclose derivativesof fatty compounds suitable in the formation of coatings. For example,acryloxymethyl substituted fatty compounds have been claimed to beuseful in radiation curable coating formulations and as binders in inks.Acrylate esters of castor oil have also been reported to be potentiallyuseful as binders in coatings and other applications.

[0010] However, none of these references discloses use of an internallyplasticizing and crosslinkable monomer derived from either a traditionalsemi-drying or a non-drying oil for the formation of coatingformulations. In addition, none of the references discussed aboveutilizes inexpensive and readily available acrylate or otherethylenically unsaturated esters of long-chain olefinic monomers derivedfrom semi- or non-drying oils to form latex or emulsion compositions.Furthermore, none of the references mentioned above describes latex oremulsion compositions featuring low MFTs that cure to above ambientT_(g) without the use of any VOCs and yet featuring enhanced properties.

[0011] Therefore, it is an object of this invention to provide novelcompositions having low VOCs and low odor which are suitable for formingcoatings, adhesives, and inks formulations comprising an internallyplasticizing and crosslinkable monomer. An additional objective of thisinvention is to provide a process for the synthesis of the novel latexor emulsion compositions. It is also an objective of this invention toprovide novel internally plasticizing and crosslinkable monomers derived(or obtained) from semi- or non-drying oils, and processes for makingthe same. Yet another objective of this invention is to provide avariety of utilities for these novel compositions. Such utilitiesinclude as a binder in coatings, adhesives, and inks formulationsfeaturing enhanced properties yet contributing zero VOCs. Thecompositions of the present invention have no precedence in the priorart.

[0012] Prior Art

[0013] The following references are disclosed as background art and forinformational purpose.

[0014] U.S. Pat. No. 4,626,582 discloses acyloxymethyl fatty compoundswhich are useful as monomers in the preparation of radiation curablecoatings.

[0015] U.S. Pat. No. 4,826,907 discloses an acrylic or methacrylic resinemulsion coating composition, and its use.

[0016] U.S. Pat. No. 4,906,684 discloses ambient curing coatingcompositions which are made from aqueous dispersions of copolymers ofacetoacetoxyethyl acrylate or methacrylate, glycidyl acrylate ormethacrylate, and ethylenically unsaturated polymerizable acid and adifferent monomer copolymerizable therewith.

[0017] Eur. Pat. Appln. No. 466,409 discloses a polymer blend useful asa binder in an aqueous coating composition containing no coalescent.

[0018] Indian Pat. No. 153,599 describes a process for preparing novelvinyl monomers from ricinoleic acid and mixed fatty acids of castor oil.

[0019] Indian Pat. No. 154,467 describes a process for the preparationof novel acrylic monomers and polymers from castor oil and methylricinoleate.

[0020]J. American Oil Chem. Soc., (1966) (pp 542-545) describessynthesis of acrylate esters of various hydroxy acid derivativesobtainable from castor oil.

[0021] Al of the references described herein are incorporated herein byreference in their entirety.

SUMMARY OF THE INVENTION

[0022] Surprisingly, it has now been found that coatings, adhesives andinks having essentially no VOCs can readily be formed from novel latexor emulsion compositions. In addition, the novel compositions of thepresent invention are comprised of a monomer which features aplasticizing property, and thus serves as an internal plasticizer andsubsequently as a crosslinking agent. The monomers suitable for formingthe latex or emulsion compositions of this invention are derivatives ofsemi- or non-drying oils having an ethylenically unsaturated ester of along-chain olefinic compound. Preferred monomers of this invention areacrylate or methacrylate esters of long-chain olefinic monomers dived(or obtained) from either castor oil or lesquerella oil. The laticesformed by this invention have utility in numerous applications such asin coatings, adhesives, and inks formulations.

[0023] Accordingly, the present invention provides a composition havinglow volatile organics content and low odor that is suitable for formingcoatings, adhesives, and inks formulations comprising an aqueousdispersion composed of a blended mixture of:

[0024] (a) a polymer obtained by the polymerization of:

[0025] (i) an internally plasticizing and crosslinkable monomer derivedfrom a semi- or non-drying oil; and

[0026] (ii) one or more of ethylenically unsaturated monomerscopolymerizable therewith;

[0027] (b) a drier selected from the group consisting of aliphaticcarboxylic acid salts of cobalt, manganese, lead, zirconium, calcium,and mixtures thereof; and

[0028] (c) a surface-active agent; wherein the total weight percent ofthe polymer in said aqueous dispersion is at least from about 5 and notmore than about 80 weight percent, wherein the monomers (i) and (ii) arepresent in the weight ratio ranging from about 1:2 to about 1:99.

[0029] In another aspect of the present invention, a process for theformation of a waterborne formulation for coatings, inks or adhesivescontaining a polymer formed from an ethylenically unsaturated ester of along-chain olefinic compound derived (or obtained) from a semi- ornon-drying oil is also provided.

[0030] In further aspects of this invention novel monomers suitable forforming the above mentioned latex or emulsion compositions, andprocesses for making these monomers are also provided.

DETAILED DESCRIPTION OF THE INVENTION

[0031] Surprisingly, it has now been found that coatings, adhesives andinks having essentially no VOCs can readily be formed from novel latexor emulsion compositions. In addition, the novel compositions of thepresent invention are comprised of a monomer which features aplasticizing property, and thus serves as an internal plasticizer. Themonomers suitable for forming the latex or emulsion compositions of thisinvention are derivatives of semi- or non-drying oils having anethylenically unsaturated ester of a long-chain olefinic compound.Preferred monomers of this invention are acrylate or methacrylate estersof long-chain olefinic monomers derived (or obtained) from either castoroil or lesquerella oil. The latices formed by this invention haveutility in numerous applications such as in coatings, adhesives, andinks formulations.

[0032] Accordingly, the present invention provides a composition havinglow volatile organic content and low odor that is suitable for formingcoatings, adhesives, and inks formulations comprising an aqueousdispersion composed of a blended mixture of:

[0033] (a) a polymer obtained by the polymerization of:

[0034] (i) an internally plasticizing and crosslinkable monomer derivedfrom a semi- or non-drying oil; and

[0035] (ii) one or more of ethylenically unsaturated monomerscopolymerizable therewith;

[0036] (b) a drier selected from the group consisting of aliphaticcarboxylic acid salts of cobalt, manganese, lead, zirconium, calcium,and mixtures thereof; and

[0037] (c) a surface-active agent;

[0038] wherein the total weight percent of the polymer in said aqueousdispersion is at least from about 5 and not more than about 80 weightpercent, wherein the monomers (i) and (ii) are present in the weightratio ranging from about 1:2 to about 1:99.

[0039] As used herein, the term internally plasticizing monomer isintended to be generic to a class of compounds wherein the monomers ofthis invention are capable of polymerizing and at the same time act as aplasticizer (i.e., “in-chain” or “internal plasticization”) for thepolymer formed therefrom. Generally, the coatings formulations contain avolatile organic solvent additive(s) that acts as a plasticizer for thepolymeric binder. The role of these volatile organic plasticizers is toreduce the apparent T_(g) of the polymer thereby permitting the coatingto form a useful film at a temperature below the real T_(g) of thepolymer. Thus, by incorporating the internally plasticizing monomers ofthe present invention, the polymers or copolymers formed in thisinvention are self plasticized with no subsequent VOC emissions. As aresult, the compositions of the present invention which are suitable forforming coatings, adhesives, and inks exhibit lower minimum film formingtemperatures (METs) than the corresponding T_(g)'s of the curedcompositions.

[0040] Additionally, the internally plasticizing monomers of the presentinvention are also capable of crosslinking during the drying process.The term crosslinking used herein is intended to mean that the monomersof the present invention are capable of bonding to itself, and/oranother compound or polymeric chain triggered by a suitable chemical orphysical reaction. In a typical coating formulation, for example, theformulation is first applied onto a desired surface and then cured bysuitable means during which time the crosslinking of the polymericbinder occurs. Thus, the monomers of the present invention may becrosslinked after forming films from the coating compositions. Curingcan be affected by a wide variety of well known techniques in the art.

[0041] The internally plasticizing and crosslinkable monomers of thepresent invention are preferably derived from semi- or non-drying oils.The term derived used herein is intended to mean that the monomers ofthe present invention are obtained or formed from a wide variety ofsemi- or non-drying oils. Various chemical and physical modifications ofthese semi- or non-drying oils may be made to obtain the desirablemonomers of the present invention using the methods well known in theart.

[0042] Various semi- and non-drying oils may be employed for theformation of the monomers of the present invention. The terms semi- andnon-drying oils used herein are defined as those oils which do not showmarked increase in viscosity on exposure to air. Generally, oils areclassified as drying, semi-drying, or non-drying based on their “iodinevalue,” that is, the number of grams of iodine required to saturate thedouble bonds of 100 grams of an oil. In accordance with this definition,oils having an iodine value of about 120 to 150 are generally consideredto be semi-drying oils, and oils having less than 120 are generallyconsidered to be non-drying oils. Illustrative examples of suchsemi-drying oils include safflower oil, sunflower oil, soybean oil, andtobaccoseed oil. Illustrative examples of such non-drying oils includecottonseed oil, coconut oil, rapeseed oil, castor oil, and lesquerellaoil. A detailed description of the classification of various oils may befound in “Surface Coatings—Raw Materials and Their Usage,” Vol., Chapmanand Hall, Chapter 4, p-45, (1993), incorporated herein by reference inits entirety.

[0043] Accordingly, the preferred internally plasticizing andcrosslinkable monomers derived from semi- or non-drying oils of thepresent invention are substituted ethylenically unsaturated carboxylicacid esters of long-chain olefinic compounds of the formula I:

[0044] wherein (a) R₁, R₂, R₃, R₄, R₅, R₆, and R₇, are the same ordifferent and are each independently selected from the group consistingof:

[0045] hydrogen;

[0046] alkoxy group having 1 to 10 carbon atoms;

[0047] alkoxyalkyl group having 1 to 10 carbon atoms; and

[0048] linear or branched alkyl and fluoroalkyl groups having theformula C_(n)H_(x)F_(y), where n is an integer from 1 to 10, x and y areintegers from 0 to 2n+1, and the sum of x and y is 2n+1;

[0049] (b) R₈ is selected from the group consisting of:

[0050] —CN;

[0051] —COOR;

[0052] —CH₂OH;

[0053] —CH₂OR;

[0054] —CONR′R″; and

[0055] —CH₂NR′R″;

[0056] where (i) R is selected from the group consisting of:

[0057] phenyl and substituted phenyl;

[0058] tolyl and substituteatolyl;

[0059] benzyl and substituted benzyl;

[0060] alkoxyalkyl group having 1 to 10 carbon atoms;

[0061] hydroxyalkyl group having 1 to 10 carbon atoms;

[0062] acyloxyalkyl group having 1 to 10 carbon atoms;

[0063] a linear or branched alkenyl group having 2 to 10 carbon atoms;

[0064] linear or branched alkyl and fluoroalkyl groups having theformula C_(n)H_(x)F_(y), where n is an integer from 1 to 10, x and y areintegers from 0 to 2n+1, and the sum of x and y is 2n+1; and

[0065] a multifunctional moiety having the structure II or III:

[0066] where R₁₂ and R₁₃ are the same or different and are independentlyselected from the group consisting of:

[0067] a substituted or unsubstituted, saturated or unsaturated fattyacid chain; acrylic and substituted acrylic;

[0068] a linear or branched alkyl or alkenyl carboxylic acid moietyhaving 2 to 30 carbon atoms; and

[0069] monoalkyl esters of maleic and fumaric acids, where alkyl groupcontains 1 to 4 carbon atoms;

[0070] (ii) R′, and R″ are the same or different and are independentlyselected from the group consisting of:

[0071] hydrogen;

[0072] phenyl and substituted phenyl;

[0073] tolyl and substituted tolyl;

[0074] benzyl and substituted benzyl;

[0075] alkoxyalkyl group having 1 to 10 carbon atoms;

[0076] hydroxyalkyl group having 1 to 10 carbon atoms;

[0077] acyloxyalkyl group having 1 to 10 carbon atoms;

[0078] a linear or branched alkenyl group having 2 to 10 carbon atoms;and

[0079] linear or branched alkyl and fluoroalkyl groups having theformula C_(n)H_(x)F_(y), where n is an integer from 1 to 10, x and y areintegers from 0 to 2n+1, and the sum of x and y is 2n+1;

[0080] (c) R₉, R₁₀, and R₁₁ are the same or different and areindependently selected from the group consisting of:

[0081] hydrogen;

[0082] a carboxylate of the formula —COOR, where R is alkyl group having1 to 10

[0083] carbon atoms, or phenyl and substituted phenyl;

[0084] phenyl and substituted phenyl;

[0085] tolyl and substituted tolyl;

[0086] benzyl and substituted benzyl;

[0087] a linear or branched alkenyl group having 2 to 10 carbon atoms;and

[0088] linear or branched alkyl and fluoroalkyl groups having theformula C_(n)H_(x)F_(y), where n is an integer from 1 to 10, x and y areintegers from 0 to 2n+1, and the sum of x and y is 2n+1; and

[0089] (d) a, a′, b, b′, and c, are integers, where a and a′ have avalue of from 0 to 10, b and b′ have a value of 0 to 2 with the provisothat sum of b and b′ is 1 or 2, and c has a value of from 0 to 20.

[0090] In the above definitions and throughout the presentspecification, alkoxy means straight or branched chain alkoxy having 1to 10 carbon atoms, and includes, for example, methoxy, ethoxy,n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, pentyloxy,hexyloxy, heptyloxy, octyloxy, nonanyloxy, decanyloxy, 4-methylhexyloxy,2-propylheptyloxy, and 2-ethyloctyloxy.

[0091] Alkoxyalkyl means that the alkoxy moiety and the alkyl moietyeach are straight or branched chains having 1 to 10 carbon atoms, andincludes, for example, methoxymethyl, ethoxymethyl, propoxymethyl,isopropoxymethyl, butoxymethyl, isobutoxymethyl, tert-butoxymethyl,pentyloxymethyl, hexyloxymethyl, heptyloxymethyl, octyloxymethyl,decyloxymethyl, 2-methoxyethyl, 2-ethyloxyethyl, 2-propoxyethyl,2-butoxyethyl, 2-hexyloxyethyl, 2-octyloxyethyl, 2-nonyloxyethyl,3-methoxypropyl, 3-ethoxypropyl, 3-propoxypropyl, 3-butoxypropyl,3-hexyloxypropyl, 3-octyloxypropyl, 3-decyloxypropyl, 4-methoxybutyl,4-ethoxybutyl, 4-propoxybutyl, 4-butoxybutyl, 4-hexyloxybutyl,4-octyloxybutyl, 4-nonyloxybutyl, 5-methoxypentyl, 5-ethoxypentyl,5-propoxypentyl, 5-butoxypentyl, 5-pentyloxypentyl, 5-hexyloxypentyl,5-octyloxypentyl, 5-decyloxypentyl, 6-methoxyhexyl, 6-ethoxyhexyl,6-propoxyhexyl, 6-butoxyhexyl, 6-pentyloxyhexyl, 6-hexyloxyhexyl,6-octyloxyhexyl, 6-decyloxyhexyl, 8-methoxyoctyl, 8-ethoxyoctyl,8-butoxyoctyl, 8-hexyloxyoctyl, 8-octyloxyoctyl, 10-methoxydecyl,10-propoxydecyl, 10-pentyloxydecyl, and 10-decyloxydecyl.

[0092] Hydroxyalkyl means a hydroxy containing straight or branchedchain alkyl group having 1 to 10 carbon atoms, and includes, forexample, hydroxymethyl, 2-hydroxyethyl, 1-hydroxyethyl, 3-hydroxypropyl,2-hydroxypropyl, 4-hydroxybutyl, 3 -hydroxy-3-methylpropyl,5-hydroxypentyl, 4-hydroxy-3-methylbutyl, 6-hydroxyhexyl,8-hydroxyoctyl, and 10-hydroxydecyl.

[0093] Acyloxyalkyl means that acyloxy moiety and the alkyl moiety eachare straight or branched chains having 1 to 10 carbon atoms, andincludes, for example, acetoxym ethyl, acryloxymethyl,methacryloxymethyl, propionoxymethyl, acetoxyethyl, acryloxyethyl,butyroxyethyl, acetoxybutyl, acryloxybutyl, hexanoyloxybutyl,acetoxyhexyl, acryloxyhexyl, octanoyloxyhexyl, acetoxyoctyl,acryloxyoctyl, acetoxydecyl, and acryloxydecyl.

[0094] Substituted phenyl, tolyl, and benzyl means phenyl, tolyl, orbenzyl ring substituted by at least one suitable substituent groupselected from the group consisting of amino, nitro, hydroxy, straight orbranched alkoxy group such as methoxy, straight or branched alkyl and/orfluoroalkyl group such as methyl, trifluoromethyl, alkenyl group such asvinyl, and halogen (fluorine, chlorine, bromine or iodine).

[0095] Representative examples of linear or branched alkyl andfluoroalkyl groups having 1 to 10 carbon atoms include, for example,methyl, trifluoromethyl, ethyl, 1,1,2-trifluoroethyl, pentafluoroethyl,propyl, perfluoropropyl, isopropyl, butyl, isobutyl, tert-butyl,perfluorobutyl, 1,1,2,3,3-pentafluorobutyl, pentyl, hexyl, heptyl,octyl, nonyl, and decanyl.

[0096] Linear or branched alkenyl means alkenyl moiety having 2 to 10carbon atoms, and includes, for example, vinyl, 1-propenyl, allyl,isopropenyl, 2-butenyl, 1,3-butadienyl, 2-pentenyl, 2-hexenyl,2-octenyl, 3-nonenyl, and 4-decenyl.

[0097] Substituted or unsubstituted, saturated or unsaturated fatty acidchain means a variety of long-chain fatty acids present in the oils asone of the triglycerides. These fatty acids may further be substitutedby one or more substituents selected from the group consisting of alkyl,alkoxy, alkoxyalkyl, hydroxy, hydroxyalkyl, acyloxyalkyl, and halogensas described hereinabove. Illustrative examples of a few of these fattyacids include oleic acid, elaidic acid, linoleic acid, linolenic acid,erucic acid, brassidic acid, nervonic acid, lauric acid, myristic acid,palmitic acid, margaric acid, stearic acid, arachidic acid, behenicacid, lignoceric acid, cerotic acid, melissic acid and undecylenic acid.

[0098] Substituted acrylic means acrylic substituted by at least onesubstituent at the α- or β- position of the acrylic chain. Such asubstituent is selected from the group consisting of methyl, ethyl,propyl, butyl, phenyl, and tolyl. Illustrative examples of substitutedacrylic include methacrylic, ethacrylic, cinnamic, crotonic,isocrotonic, tiglic, and angelic.

[0099] A wide variety of linear or branched alkyl or alkenyl carboxylicacid moieties (as R₁₂ and R₁₃) having 2 to 30 carbon atoms are suitablefor forming the internally plasticizing monomers of the presentinvention containing the multifunctional moiety II or III. Examples ofsuch acids include acetic acid, propionic acid, n-butyric acid,n-hexanoic acid, n-heptanoic acid, octanoic acid, nonanoic acid,decanoic acid, lauric acid, myristic acid, palmitic acid, margaric acid,stearic acid, arachidic acid, behenic acid, lignoceric acid, ceroticacid, melissic acid and the like. Various other unsaturated fatty andnon-fatty acids including the acrylic and substituted acrylics mentionedabove may also be employed.

[0100] Monoalkyl esters of maleic and fumaric acids include, forexample, methyl hydrogen maleate, methyl hydrogen fumarate, ethylhydrogen maleate, ethyl hydrogen fumarate, propyl hydrogen maleate,propyl hydrogen fumarate, butyl hydrogen maleate, and butyl hydrogenfumarate.

[0101] Furthermore, and as used herein, the term “substituted” iscontemplated to include all permissible substituents of organiccompounds. In a broad aspect, the permissible substituents includeacyclic and cyclic, branched and unbranched, carbocyclic andheterocyclic, aromatic and non-aromatic substituents of organiccompounds. Illustrative substituents include, for example, thosedescribed hereinabove. The permissible substituents can be one or moreand the same or different for appropriate organic compounds. Forpurposes of this invention, the heteroatoms such as nitrogen may havehydrogen substituents and/or any permissible substituents of organiccompounds described herein which satisfy the valencies of theheteroatoms. This invention is not intended to be limited in any mannerby the permissible substituents of organic compounds.

[0102] As mentioned earlier, the preferred internally plasticizingmonomers of this invention are derived (or obtained) from semi- ornon-drying oils; that is, semi- or non-drying oils are subjected tosuitable chemical or physical transformations to obtain these monomers.These starting materials may be obtained from natural sources such asvegetable or animal sources or may be synthetic. Thus, the startingmaterials which may be converted to the desired internally plasticizingmonomers of this invention contain at least one hydroxy group in theirbackbone and have a terminal polar moiety (i.e., R₈ in I) selected fromthe group consisting of —CN, —COOR, —CH₂OH, —CH₂OR, —CONR′R″, and—CH₂NR′R″ where R, R′, and R″ have the same meaning as defined above.These terminal polar moieties may be introduced, if necessary, into thecompounds obtained from semi- or non-drying oils using a number ofwell-known methods in the art. A description of a few of such methodsmay be found in U.S. Pat. No. 4,356,128 to Rogier, incorporated hereinby reference in its entirety.

[0103] Briefly, the starting materials containing the terminal group,—COOR may be obtained by subjecting the oil to suitabletransesterification reaction in the presence of an alcohol ROH. In thisinstance, the oil which is a triglyceride may also be used as such.Triglycerides are triesters of a glycerol formed by a combination of oneor more fatty acids, and thus R in this case is a multifunctional moietyas defined above (i.e., II or III). The fatty compounds containing—CH₂OH or —CH₂OR terminal groups may be obtained by subjecting thecorresponding fatty ester to suitable reductive conditions. Ifnecessary, other groups vulnerable to such reductive conditions maysuitably be protected before subjecting the fatty ester to reductiveconditions.

[0104] Similarly, compounds having —CONR′R″ (i.e., amides) may beobtained by the reaction of corresponding carboxylic acids (or thecarboxylic acid halides such as carboxylic acid chloride) obtained fromthe oils with an amine, HNR′R″ under suitable reaction conditions.Further subjecting so formed amides to suitable reduction reactionsresults in the formation of compounds having —CH₂NR′R″ group.

[0105] The compounds with the —CN group, for example, may be obtained byfirst reacting the fatty acid chlorides with ammonia to form thecorresponding amides having the terminal group, —CONH₂. The amides soformed can subsequently be dehydrated using a number of well-knowndehydrating agents known in the art to form the corresponding —CNcontaining compounds.

[0106] The preferred hydroxy fatty acids that are suitable for formingthe long-chain olefinic ester I may be selected from the groupconsisting of ricinoleic, lesquerolic, auricolic, and densipolic acid.All of these acids contain one hydroxy group and at least one doublebond in their back bone. If the starting material employed in the latexor emulsion compositions of the present invention is a triglyceride,then various other fatty acids may be employed as R₁₂ and R₁₃ in thetriglyceride (i.e., II or III). The preferred fatty acids that may beemployed for forming the desired triglycerides may be selected from thegroup consisting of oleic, linoleic, erucic, and vernolic acid.

[0107] However, the fatty acids obtained from the drying oils as suchare not suitable for forming the triglycerides that are suitable asstarting materials of this invention (i.e., I). In general, fatty acidscontaining more than two double bonds in their back bone are notsuitable starting materials for this invention without furtherderivation as described hereinbelow. Such fatty acids, for example,include linolenic, eleostearic, licanic, and isanic acid. Accordingly,the non-drying oils are generally more preferred in this invention andinclude, for example, cottonseed, coconut, rapeseed, lesquerella,castor, and vernonia oil. The non-drying oils which contain no hydroxygroups in their backbone may be suitably functionalized so as to resultin at least one hydroxy group in their backbone. For example, U.S. Pat.No. 4,626,582 describes synthesis of hydroxymethyl containing fattycompounds; and U.S. Pat. No. 5,312,889 describes formation of a hydroxygroup using an unsaturated fatty compound by epoxidation and reductivering opening, which are incorporated herein by reference in theirentirety. Similarly, drying oils can be suitably transformed intohydroxy fatty acids or their derivatives having an iodine value of 150or less such that they can be used as semi- and/or non-drying oilcomponents of this invention. Particularly preferred non-drying oils arecastor and lesquerella oils.

[0108] A wide variety of ethylenically unsaturated carboxylic acids orits derivatives may be used for the formation of desired startingmaterials of the present invention. The carboxylic acids having at leastone polymerizable ethylenic bond per molecule (i.e., a double bond) arepreferred. The acids with an ethylenic bond α,β- (i.e., 1,2-) to thecarboxylic group are particularly preferred. Representative examples ofsuch ethylenically unsaturated carboxylic acids include, withoutlimitation, acrylic, methacrylic, maleic, fumaric, itaconic, ethacrylic,crotonic, citraconic, cinnamic, methyl hydrogen fumarate, benzylhydrogen maleate, butyl hydrogen maleate, octyl hydrogen itaconate, anddodecyl hydrogen citraconate. If the acid employed is a dicarboxylicacid, such as maleic acid or fumaric acid, then the resulting startingmaterial is a diester of a desired long-chain olefinic monomer.

[0109] The compositions containing the long-chain olefinic monomers ofthe present invention further consists of at least one copolymerizablemonomer. Such a copolymerizable monomer include, broadly, polymerizableacid monomer, a monomer containing at least one ethylenicallyunsaturated polymerizable group, and various other ethylenicallyunsaturated monomers well known in the art.

[0110] Polymerizable acid monomers used in this invention are the wellknown mono- or polycarboxylic acids which contain one polymerizable bondper molecule. Examples of such acids are acrylic acid, methacrylic acid,maleic acid, fumaric acid, itaconic acid, ethacrylic acid, crotonicacid, citraconic acid, and half esters of the dicarboxylic acids whereinthe esterified alcohol group contains from 1 to about 20 carbon atoms.Examples of suitable half esters are methyl hydrogen maleate, methylhydrogen fumarate, benzyl hydrogen maleate, butyl hydrogen maleate,octyl hydrogen itaconate, dodecyl hydrogen citraconate, and the like.Carboxylic acid anhydrides such as maleic anhydride can also be used.The preferred acids for use in this invention are acrylic andmethacrylic acids.

[0111] Copolymerizable monomers that contain at least one ethylenicallyunsaturated polymerizable group referred to hereinabove are any of thewell known monomers which contain at least one ethylenically unsaturatedpolymerizable group per molecule and are copolymerizable with the othermonomers. Examples of such monomers are acrylic and methacrylic esterswherein the ester group contains 1 to about 20 carbon atoms, e.g.,methyl acrylate, methyl methacrylate, ethyl acrylate, ethylmethacrylate, isopropyl acrylate, isopropyl methacrylate, butylacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, decyl acrylate,lauryl methacrylate, benzyl acrylate, and the like. Esters of variousother unsaturated acids include butyl fumarate, octyl fumarate, butylmaleate, and octyl maleate.

[0112] Other acrylic or methacrylic esters which can be used in thisinvention are multifunctional acrylates or methacrylates, and includes,for example, propylene glycol monoester of acrylic acid, propyleneglycol monoester of methacrylic acid, ethylene glycol monoester ofacrylic acid, ethylene glycol monoester of methacrylic acid, glycidylacrylate, glycidyl methacrylate, hydroxyethyl acrylate, hydroxyethylmethacrylate, and hexanediol diacrylate.

[0113] Other copolymerizable monomers are vinyl aromatic monomers, suchas styrene, para-acetoxystyrene, vinyl toluene, alpha methyl styrene,vinyl pyridine and the like as well as nitriles and amides, e.g.,acrylonitrile and acrylamide. Other olefinic monomers such as ethylene,propylene, and butadiene are also suitable comonomers for thisinvention.

[0114] Additional copolymerizable monomers that can be used in thisinvention are the derivatives of the hypothetical vinyl alcohol, i.e.,aliphatic vinyl esters such as vinyl formate, vinyl acetate, vinylpropionate, vinyl butyrate, vinyl heptanoate, vinyl pelargonate, vinyl3,6-dioxaheptanoate, vinyl 3,6,9-trioxaundecanoate, the vinyl ester ofversatic acid (sold under the tradename Veova 10™), vinyl esters of neoacids and the like. Other vinyl monomers such as vinyl chloride, vinylsulfonate, vinyl silanes, and vinylidene chloride are also suitablecomonomers.

[0115] Various other copolymerizable monomers that impart enhancedproperties to the resulting compositions of the present invention mayalso be used. One such example is a wet adhesion promoter which improvesadhesion of the compositions to a wide variety of substances includingwood, plastic, and metal surfaces. Illustrative examples of such wetadhesion promoting monomers include dimethylaminoethyl methacrylate,methacrylamidoethylethyleneurea (sold under the tradename Sipomer® WAMII by Rhone-Poulenc), acrylamidoethylethyleneurea, 3-isopropenyl-α,α-dimethylbenzyl isocyanate, and styrene sulfonate.

[0116] Any monomers which are copolymerizable with the ethylenicallyunsaturated long-chain olefinic monomer I of this invention can be usedin this invention. Such monomers are those which contain no groups whichare reactive under polymerization conditions with carboxylic acidgroups, —COOR, —CH₂OH, —CH₂OR, —CN, —CONR′R″, or —CH₂NR′R″ groups. Thus,suitable comonomers may be employed depending upon the groups present inthe long-chain olefinic monomer I.

[0117] The types and amounts of copolymerizable monomers used in thisinvention will vary depending on the particular end use for which theproduct of this invention is intended. Such variations are well knownand can be readily determined by those skilled in the art. In general,the weight percents of the internally plasticizing compound, i.e., thelong-chain olefinic monomer I and the copolymerizable monomer in theresulting composition ranges from about 5 and not more than about 80weight percent based upon the total weight of the composition.Preferably, the total weight percents range from about 30 to about 70weight percent based on the total weight of the composition. The weightratio of the long-chain olefinic monomer I to the copolymerizablemonomer (s) generally range from about 1:2 to about 1:99, preferably theweight ratio range from about 1:7 to about 1:20.

[0118] In addition to the polymeric resins formed from the monomer I andthe comonomers mentioned hereinabove, the coatings or adhesives or inkscompositions of the present invention contain at least one drier. Thedriers are materials that promote or accelerate the curing or hardeningof film formers. Typically, driers are used in conjunction with coatingsformulations containing the drying oil components. Surprisingly, it hasnow been found that the metal driers are particularly effective incuring the compositions of the present invention which contain semi- ornon-drying oil components.

[0119] The suitable drier is any material which will function as apromoter or an accelerator for the curing or hardening of the film andincludes, without limitation, neutral soaps of the formula(R_(x)—COO)₂M²⁺ or (R_(x)—COO⁻)₃M³⁺; acid soaps of the formula(R_(x)—COO⁻)₂M²⁺. R_(x)—COOH or (R_(x)—COO⁻)₃M³⁺. R_(x)—COOH; basicsoaps of the formula (R_(x)—COO⁻)₂M²⁺. OH; organic complexed or mixedsoaps of the formula (R_(x)—COO⁻)(R′_(x)—COO⁻)M²⁺ or(R_(x)—COO⁻)(R′_(x)—COO⁻)(R″_(x)—COO⁻)M³⁺; inorganic/organic complexedor mixed soaps of the formula O—M²⁺ —O—CO—R_(x), X—O—M²⁺ —O—CO—R_(x),and O—M²⁺ —O—CO—R_(x); where R_(x)—COO⁻, R′_(x)—COO⁻; and R″_(x)—COO⁻are aliphatic carboxylic acid ions having 6 to 20 carbon atoms, M=metalion, and X=phosphorus or boron.

[0120] The commonly used carboxylic acids for forming the metal driersare aliphatic acids, preferably fatty acids. Illustrative examples offatty acids include rosin oil fatty acid, linseed oil fatty acid, andtall oil fatty acid. Various naphthenic acids obtained from certainpetroleum crudes may also be used for forming the suitable metal driers.The naphthenic acids generally contains an average of 12-14 carbon atomshaving a cyclopentane nucleus with the carboxyl group terminating a sidechain and with one to three methylenic groups between the carboxyl andthe nucleus. Various other synthetic acids having 8 to 10 carbon atomsare also used to form the metal driers, and include, for example,2-ethylhexanoic acid and neodecanoic acids.

[0121] The most commonly used drier metals are cobalt, zirconium,manganese, calcium and lead. Other metals such as zinc, copper, barium,vanadium, cerium, iron, potassium, strontium, aluminum, bismuth, andlithium have also been used as drier metals. Particularly preferredmetal driers are aliphatic carboxylic salts of cobalt, manganese, lead,zirconium, calcium, and mixtures thereof It has been found that cobaltsalts sold under the tradename Co Hydro-Cure® II are particularlypreferred metal driers for the compositions of the present invention. Adetailed description of various metal driers may be found in “SurfaceCoatings—Raw Materials and Their Usage,” Vol. I, Chapman & Hall, Chapter33, pp 592-606 (1993), incorporated herein by reference in its entirety.

[0122] Although metal driers mentioned hereinabove are particularlyeffective in the drying of the films, various other non-metallic drierswell-known in the art may also be employed either as primary driers,auxiliary driers, or as drier accelerators. Many auxiliary non-metallicdriers are effective in improving the solubility of the active driermetal in the reactive medium or alter the drier metals' redox potential.Examples of such non-metallic driers include 8-hydroxyquinoline,quinoline, salicyl aldoxime, pyridine-2-carbaldoxime, acetylacetonateenamines, 2-2′-bipyridyl, ethylenediamine, propylenediamine, pyridine,o-vinylpyridine, o-aminopyridine, aniline, o-phenylenediamine,o-toluidine, α-naphthylamine, o-phenanthroline, dipropylamine,diamylamine, acrylonitrile, succinonitrile, o-tolunitrile, o-toluamide,o-tolyl isocyanate, phenyl isocyanate, naphthyl isocyanate, pyrrole,benzimidazole, benzotriazole, and the like. Particularly preferrednon-metallic drier is 2-2′-bipyridyl sold under the tradename DRI-RX™.

[0123] As described hereinbelow, the compositions of this invention areprepared by polymerization of monomers emulsified in water usingconventional emulsion polymerization procedures. A suitablesurface-active agent generally known as surfactants are used foremulsification of the monomers. Suitable surfactants include cationic,anionic, amphoteric, or nonionic surfactants or mixtures thereof.

[0124] Examples of useful anionic surfactants are organosulfates andsulfonates, e.g., sodium and potassium alkyl, aryl, and aralkyl sulfatesand sulfonates, such as sodium 2-ethylhexyl sulfate, potassium2-ethylhexyl sulfate, sodium nonyl sulfate, sodium lauryl sulfate,potassium methylbenzene sulfonate, sodium dodecylbenzene sulfonate,potassium toluene sulfonate and sodium xylene sulfonate; higher fattyalcohols, e.g., stearyl, lauryl, etc., which have been ethoxylated andsulfonated; dialkyl esters of alkali metal sulfosuccinic acid salts,such as sodium diamyl sulfosuccinate, sodium dioxtyl sulfosuccinate, andsodium dioctyl sulfosuccinate, formaldehyde-naphthalene sulfonic acidcondensation products; and alkali metal salts, partial alkali metalsalts and free acids of complex organic phosphate esters.

[0125] Examples of useful cationic surfactants include alkylamine saltssuch as laurylamine acetate, quaternary ammonium salts such as lauryltrimethyl ammonium chloride and alkyl benzyl dimethylammonium chlorides,and polyoxyethylenealkylamines. Examples of the amphoteric surfactantsare alkylbetaines such as lauryl-betaine.

[0126] Examples of nonionic surfactants which can be used in thisinvention are polyethers, e.g., ethylene oxide and propylene oxidecondensates which include straight and branched chain alkyl and alkarylpolyethylene glycol and polypropylene glycol ethers and thioethers;alkylphenoxypoly(ethyleneoxy) ethanols having alkyl groups containingfrom about 7 to about 18 carbon atoms and having from about 4 to about240 ethyleneoxy units, such as heptylphenoxypoly(ethyleneoxy) ethanols,nonylphenoxypoly(ethyleneoxy) ethanols; the polyoxyalkylene derivativesof hexitol including sorbitans, sorbides, mannitans and mannides;partial long-chain fatty acids esters, such as the polyoxyalkylenederivatives of sorbitan monolaurate, sorbitan monopalmitate, sorbitanmonostearate, sorbitan tristearate, sorbitan monooleate and sorbitantrioleate; the condensates of ethylene oxide with a hydrophobic base,said base being formed by condensing propylene oxide with propyleneglycol; sulfur containing condensates, e.g., those prepared bycondensing ethylene oxide with higher alkyl mercaptans, such as nonyl,dodecyl, or tetradecyl mercaptan, or with alkylthiophenols wherein thealkyl group contains from about 6 to about 15 carbon atoms; ethyleneoxide derivatives of long-chain carboxylic acids, such as lauric,myristic, palmitic, or oleic acids or mixtures of acids, such as talloil fatty acids; ethylene oxide derivatives of long-chain alcohols suchas octyl, decyl, lauryl, or cetyl alcohols; and ethylene oxide/propyleneoxide copolymers sold under the tradename Pluoronics™.

[0127] A particularly useful surfactant which can be used in thisinvention is a nonionic surfactant which is an organosilanol derivativeof tung oil, or linseed oil, or high erucic acid rapeseed oil. Thesesurfactant compositions particularly feature high surface activity informing stable emulsions of organic/water of various difficultlyemulsifiable materials as compared with conventional emulsifying agents.These silanol-based surfactant compositions are described in copending,commonly assigned patent application Ser. No. 08/739,850, filed Oct. 30,1996. Another class of preferred surfactants are those which arecopolymerizable with the monomers described hereinabove.

[0128] The amounts of surfactants employed in the emulsionpolymerization process will range from about 0.01 to about 10 weightpercent, preferably about 0.2 to about 5 weight percent based on thetotal weight of monomers and water.

[0129] The compositions of the present invention may contain in additionto the polymeric resins and metal driers referred to hereinabove, asrequired, suitable additives such as protective colloids, fillers,coloring agents, antiseptics, biocides, dispersing agents, thickeningagents, thixotropic agents, antifreezing agents, and pH adjustingagents.

[0130] Examples of protective colloids are partially and fullyhydrolyzed polyvinyl alcohol, hydroxyethyl cellulose, hydroxymethylcellulose, ethylhydroxyethyl cellulose, carboxymethyl cellulose,ethoxylated starch derivatives, polyacrylic acid, alkali metalpolyacrylates, polyacrylamide, poly(methyl vinyl ether/maleicanhydride), polyvinylpyrrolidone, water soluble starch, glue, gelatin,water soluble alginates, guar, gum arabic and gum tragacanth. Theamounts of protective colloids used in the composition varies dependingupon the intended application and generally ranges from about 0.1 weightpercent to about 2 weight percent based on the total weight of thecomposition.

[0131] Examples of fillers include talc, calcium carbonate, diatomaceousearth, mica, kaolin, barium sulfate, magnesium carbonate, Aerosil,vermiculite, graphite, alumina, silica and rubber powder. Such coloringagents as titanium dioxide and carbon black can also be used as thefillers. The amount of the filler may be properly selected, and whenused, for example, ranges from about 10 weight percent to about 50weight percent based on the total weight of the composition of thepresent invention.

[0132] Various organic pigments and inorganic pigments may be broadlyused as the coloring agents, but non-toxic anticorrosive pigments arepreferred. Examples of such pigments are phosphate-type anticorrosivepigments such as zinc phosphate, calcium phosphate, aluminum phosphate,titanium phosphate, silicon phosphate, and ortho- and fused phosphatesof these; molybdate-type anticorrosive pigments such as zinc molybdate,calcium molybdate, calcium zinc molybdate, potassium zinc molybdate,potassium zinc phosphomolybdate and potassium calcium phosphomolybdate;and borate-type anticorrosive pigments such as calcium borate, zincborate, barium borate, barium meta-borate and calcium meta-borate. Theamount of the coloring agent used may also be properly selected based onthe end-use application of the compositions of the present invention.

[0133] Examples of the antiseptics are pyrrole compounds, imidazolecompounds, thiazole compounds, pyridine compounds and organic halogencompounds. The amount of the antiseptic can be suitably selected, andis, for example, up to about 4 percent by weight based on the totalweight (as solids content) of the composition.

[0134] Examples of the biocides, which are used either as wet-stateprotectors (i.e., in-can protectors) or as film protectors of a coatingcomposition, are a wide variety of bactericides, fungicides oralgicides, and include, without limitation, zinc oxide, cuprous oxide,organotin pigments, copolymers of organotin esters of methacrylic acidwith conventional acrylates, tributyl tin oxide, and mixtures thereofOther examples of biocides particularly useful as in-can protectors areoxazoladines, organosulfurs, and benzisothiazolins. Any general toxicagent may be suitable as a biocide.

[0135] The dispersing agents may, for example, be inorganic dispersingagents such as sodium salts of polycarboxylic acids, sodium or ammoniumsalt of fused naphthalene sulfonate, polyoxyalkylene alkyl ethers ofphenol ether, sorbitan fatty acid esters, polyoxyalkylene fatty acidesters, glycerin fatty acid esters, polyoxyethylene styrene phenol,sodium tripolyphosphate and sodium hexametaphosphate. As mentionedabove, novel organosilanol derivatives of tung oil, or linseed oil, orhigh erucic acid rapeseed oil which are useful as surfactants are alsosuitable as dispersing agents. The amount of the dispersing agent canagain be properly selected depending on the end application of thecomposition, and may range up to about 10 weight percent based on thetotal weight of the composition.

[0136] The thickening and thixotropic agents may be one and the same ordifferent and may be the same as the protective colloids referred tohereinabove. Examples of thickening or thixotropic agents are polyvinylalcohol, cellulose derivatives such as hydroxyethyl cellulose,hydroxypropyl cellulose and carboxymethyl cellulose salt, polyethercompounds, urethane-modified polyether compounds, polycarboxylic acidcompounds, sodium salts of polycarboxylic compounds,polyvinylpyrrolidone, polyoxyethylene derivatives such as polyethyleneglycol ether and polyethylene glycol distearate, sodium alginate andinorganic materials such as sodium silicate and bentonite. The amountsof the thickening or the thixotropic agents can be properly chosendepending upon the type of end-application of the composition of thepresent invention.

[0137] Examples of the pH adjusting agents are sodium hydroxide,potassium hydroxide, sodium hydrogen carbonate, ammonia,triethanolamine, and β-dimethylaminoethanol. The amount of the pHadjusting agent may be a suitable one which is sufficient to adjust thepH of the composition to a desired value.

[0138] Various other additives having functional applications incoatings which are well known to those skilled in the art may also beused with the compositions of the present invention. Specific examplesof such functional additives are corrosion inhibitors, ultraviolet lightstabilizers, antioxidants, and the like.

[0139] Thus, in one of the specific embodiments of this invention thetotal solids content including the internally plasticizing compound,i.e., the long-chain olefinic monomer I, copolymerizable monomers, andall of the desirable additives referred to hereinabove is preferablyranging from about 30 to about 70 percent by weight based on the totalweight of the composition.

[0140] In another specific embodiment of this invention, the compositionsuitable for forming latex or emulsion coatings comprises an internallyplasticizing compound derived (or obtained) from a non-drying oil havinga substituted ethylenically unsaturated carboxylic acid ester of along-chain olefinic ester of the formula IV.

[0141] Where R and R₉ are as defined above, however, preferably R iseither methyl or multifunctional moieties II or III. Preferred R₉ iseither hydrogen or methyl, i.e., ethylenically unsaturated ester in thispreferred embodiment is either acrylic or methacrylic ester. a, a′, b,b′, and c, in structure IV are integers, where a and a′ have a value offrom 2 to 4, b and b′ have a value of 0 to 2 with the proviso that sumof b and b′ is 1 or 2, and c has a value of 5 to 12.

[0142] The preferred copolymerizable monomers in this embodiment may beselected from the group consisting of vinyl acetate, vinyl chloride,vinyl ester of versatic acid, acrylonitrile, acrylamide, 2-ethylhexylacrylate, 2-ethylhexyl methacrylate, 2-hydroxyethyl acrylate,2-hydroxyethyl methacrylate, glycidyl acrylate, glycidyl methacrylate,acrylic acid, butyl acrylate, butyl methacrylate, methyl methacrylate,methyl acrylate, and styrene. Various combinations of one or more ofanionic, cationic, amphoteric, or nonionic surfactants may be used inthis embodiment.

[0143] The starting materials for the preferred long-chain olefinicester IV in the above embodiment is derived (or obtained) from eithercastor oil or lesquerella oil, or the transesterified product obtainedfrom either castor oil or lesquerella oil with methanol. Thus, thelong-chain olefinic ester IV may be formed from appropriate startingmaterial by subjecting it to suitable esterification reaction asdescribed below.

[0144] Thus, the preferred starting material for the formation of IV maybe selected from the group consisting of castor oil, lesquerella oil,transesterified product of castor oil with methanol, transesterifiedproduct of lesquerella oil with methanol, methyl ricinoleate, and methyllesquerolate. Accordingly, the products formed from these startingmaterials which are the preferred long-chain olefinic esters IV areacrylate ester of methyl ricinoleate, methacrylate ester of methylricinoleate, acrylate ester of methyl lesquerolate, and methacrylateester of methyl lesquerolate.

[0145] As stated earlier, by incorporation of the internallyplasticizing monomers (i.e., I or IV) into compositions of the presentinvention, the compositions exhibit lower METs and cure to resins havingT_(g)s significantly higher than the MFTs. A further significance ofthis invention is the capability of tailoring the glass transitiontemperature (T_(g)) of the emulsion polymers and the MFTs of thecompositions formed therefrom. The METs of a coating composition isdetermined experimentally by using an apparatus described by Protzman etal. in J. Appl. Polymer Sci., 4, 81 (1960) incorporated herein byreference in its entirety. This apparatus is essentially an aluminumslab in which a constant and uniform temperature gradient may bemaintained. The coating composition to be measured is spread uniformlyin one of several sample wells. The point at which the film becomesdiscontinuous when dry is observed and this temperature is recorded asthe MFT. To ensure that the films are actually continuous when formedabove the MFT, the films are scrapped with a knife edge moving in thedirection from low to high temperature. Below the MFT the material chipsoff the bar easily but above the MET the coating does not lift off thebar. The transition between easily chipped to strong coating takes placeat the MFT.

[0146] Conventional latex polymers generally feature MFTs closer totheir T_(g). Contrary to this conventional norm, the compositions of thepresent invention exhibit MFTs much below the final T_(g) of the curedand crosslinked emulsion polymer contained therein, thus eliminating theneed for a plasticizer which is generally a volatile organic compound(VOC). Particularly, the compositions of the above mentioned preferredembodiment forms film at low MFTs ranging from about −5 to about 10° C.and cures to a resin having a T_(g) higher than 25° C.

[0147] The compositions of the present invention are particularly usefulas coatings, adhesives, and inks formulations. A wide variety of coatingformulations may be formed from the compositions of this invention. Ingeneral, the coating compositions are formed by incorporating theemulsion polymers formed from the internally plasticizing compound withone or more of the copolymerizable monomers described hereinabove. Inaddition, the coating compositions contain at least one drier and asurfactant, and as required, one or more of the additives describedhereinabove.

[0148] The coatings produced by the cure of the internally plasticizingcompound of this invention are useful in a wide variety of applications,i.e., architectural, decorative, maintenance, or industrial coatings.For example, in the electronics area these materials have applicationsas non-conductive coatings, e.g., solder masks for circuit boards ormoisture resistant coatings for the boards or optical fibers.

[0149] Similarly, the compositions of the present invention may beformulated into a wide variety of adhesives and inks formulations havinga diverse variety of applications. For example, in inks formulations theemulsion polymers of this invention are useful as binders. In generalink formulation differs from coating formulations in terms of theamounts of crosslinking monomers used, i.e., ink formulations generallycontain higher amounts of the crosslinker. In addition, ink formulationsmay contain higher amounts of driers and drier accelerators for fastdrying of these formulations. Accordingly, an ink formulation containingthe emulsion polymers of this invention may be obtained by adding one ormore pigments to the emulsion in accordance with a well-known method.The compositions of this invention may also be employed in formingradiation curable formulations, for example, UV curable high glosscoatings, inks, and adhesives formulations.

[0150] An adhesive formulation containing the emulsion polymers of thisinvention may similarly be obtained in accordance with a well -knownmethod. Typically, an adhesive formulation may be formed using theemulsion polymer of this invention in combination with one or more ofsurfactants, protective colloids, and one or more of various otheradditives discussed hereinabove. The adhesive formulations of thisinvention are particularly suitable in the form of emulsion and/oraqueous solution, however, dry-mix, hot-melt, or solutions in organicsolvent can also be formed using the polymers of this invention. Adetailed description of adhesive formulations can be found in “Handbookof Adhesives,” 2nd Ed., edited by I. Skiest, Chapter 28, pp 465-494(1977), Van Nostrand Reinhold Co., incorporated herein by reference inits entirety.

[0151] In a further aspect the invention provides a process for theformation of a waterborne formulation for coatings, inks or adhesivescontaining a latex formed from an ethylenically unsaturated ester of along-chain olefinic monomer derived from a semi- or non-drying oilcomprising the steps of:

[0152] (a) subjecting a substituted long-chain olefinic compound havinga hydroxy group to suitable esterification conditions in the presence ofan ethylenically unsaturated carboxylic acid or its suitable derivativefor a sufficient period of time and under suitable conditions oftemperature and pressure to form the corresponding ethylenicallyunsaturated ester of a long-chain olefinic monomer;

[0153] (b) subjecting said ester of a long-chain olefinic monomer tosuitable polymerization conditions in the presence of at least one otherethylenically unsaturated copolymerizable monomer for a sufficientperiod of time and under suitable conditions of temperature and pressureto form the corresponding polymer dispersed in an aqueous phase; and

[0154] (c) blending said dispersion of said polymer with at least onedrier selected from the group consisting of aliphatic carboxylic acidsalts of cobalt, manganese, lead, zirconium, calcium, and mixturesthereof, and in the presence of at least one ionic or non-ionicsurface-active agent to form the formulation.

[0155] The starting material, i.e., the long-chain olefinic compound Vis the same compound as described hereinabove and is derived (orobtained) from a semi- or non-drying oil.

[0156] Where R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, a, a′, b, b′, and c are asdefined above. The preferred starting materials are those havingR₈=—COOR and most preferably derived (or obtained) from the groupconsisting of ricinoleic, lesquerolic, auricolic, and densipolic acids.These fatty acids are preferably obtained from non-drying oils such ascastor oil or lesquerella oil.

[0157] The esterification reaction of V and an ethylenically unsaturatedcarboxylic acid or its derivative VI may be carried out using any of thewell-known methods in the art. In the structure VI, R₉, R₁₀, and R₁₁ areas defined above. X is selected from the group consisting of Br, Cl,hydroxy, alkoxy group having 1 to 4 carbon atoms, and acyloxy group sameas the acyloxy group derived from said etbylenically unsaturatedcarboxylic acid or an acyloxy group having 2 to 4 carbon atoms asdescribed hereinabove.

[0158] Accordingly, the esterification reaction in the step (a) of theprocess of the present invention may be generically represented asfollows:

[0159] In this schematic representation, R′—CO is an acyl group of theethylenically unsaturated carboxylic acid or its derivatives of formulaVI, R−O— refers to the alkoxy group and R′″—COO refers to the acyloxygroup mentioned hereinabove. In most instances the esterificationreaction is carried out by using one mole of the acid or its derivativeVI per mole of hydroxy group present in V. However, it may be desirableto use one of these starting materials in excess of the other in somecases.

[0160] The preferred ethylenically unsaturated carboxylic acid and itsderivatives VI are either acrylic or methacrylic derivatives, i.e., R₁₀and R₁₁ are hydrogen and R₉ is either methyl or hydrogen in VI.Accordingly, the preferred acryloyl or methacryloyl compound used toesterify the hydroxy long-chain compound V is a halide such as acryloylchloride, methacryloyl chloride, acryloyl bromide, and methacryloylbromide. Various other acryloyl or methacryloyl derivatives that may beemployed in this esterification reaction include acrylic acid,methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate,ethyl methacrylate, n-propyl acrylate, butyl acrylate, acrylicanhydride, methacrylic anhydride, mixed anhydrides of acrylic and aceticacids, and the like.

[0161] The esterification reaction may be carried out with or withoutany catalysts. However, in some cases it is preferable to carry out theesterification reaction in the presence of a suitable acid, base ormetal catalysts. Any acid, base or metal catalyst that will function asa catalyst for the esterification conditions may be used in this step(a) of the process of the present invention. Specific examples of suchesterification reactions may be found in U.S. Pat. Nos. 4,745,213 and5,243,069, incorporated herein by reference in their entirety.

[0162] The suitable acid includes, without limitation, mineral acidssuch as HCI and H₂SO₄; super acids such as hydrofluoric acid,fluorosulfonic acid; organic sulfonic acids such as p-toluene sulfonicacid, methane sulfonic acid, and trifluoromethane sulfonic acid; otherinorganic acids such as phosphoric acid, and boric acid; carboxylicacids such as trifluoro acetic acid; Lewis acids such as BF₃, AlCl₃,SbF₅, and the like; and solid acid catalysts such as silica, zeolites,and the like. The suitable base includes an inorganic base such as ametal hydroxide, preferably an alkali metal hydroxide, an alkali metalcarbonate, e.g., K₂CO₃; an alkali metal alkoxide (an ionic organicbase), such as NaOCH₃, KOC(CH₃)₃, etc.; an alkali metal organic salt (anionic organic base) such as potassium acetate, etc.; and an amine (anon-ionic organic base) such as pyridine, or a tri-lower-alkylamine,e.g., tripropylamine, trimethylamine, triethylamine, an hindered basesuch as 2,4-diazabicyclo[2,2,2]octane, etc. Ammonia can also be used asa base in step (a) of the process of the present invention.

[0163] Illustrative examples of metal catalysts that are particularlysuitable in the transesterification type reactions (i.e., Eq. 2) includederivatives of Group I metals, derivatives of Group IVA metals,derivatives of Group IVB metals, derivatives of manganese and cobalt,and mixtures thereof These may be preferably lithium acetate, sodiumacetate, potassium acetate, cesium acetate, stannic acid, butylstannoicacid, stannous octanoate, dibutyltin oxide, tin butoxide, dibutyltindiesters, di-n-butyl tin dilaurate, titanium tetrabutoxide, titaniumpropoxide, titanium phenoxide, zirconium butoxide, silicon phenoxide,manganese acetate, cobalt acetate, and mixtures thereof.

[0164] The amount of the catalyst employed depends upon the nature ofthe esterification reaction and the catalyst. Any amount of catalystthat would be sufficient to carry out the desired esterificationreaction may be used and may range from about 30 parts per million toone to two moles of catalyst per mole of the acid or its derivative VIused in this reaction.

[0165] The temperature at which step (a) is conducted ranges from about−10° C. to about 150° C., preferably from about 10° C. to about 100° C.The pressure in this step (a) is not critical and can be subatmospheric,atmospheric, or super atmospheric.

[0166] The reaction times in step (a) will generally range from about 15minutes to about 6 hours or longer and sometimes under an inertatmosphere such as nitrogen.

[0167] Using the procedure of step (a) outlined herein, the hydroxylong-chain olefinic compound V undergoes esterification reaction withcarboxylic acid or its derivatives VI to form the correspondingethylenically unsaturated ester of a long-chain olefinic monomer I.

[0168] In step (b) of the process of the present invention the olefinicmonomer I is subjected to suitable emulsion polymerization conditions inthe presence of one or more of suitable copolymerizable monomers havingat least one polymerizable ethylenically unsaturated double bond. Thesuitable copolymerizable monomers of this invention are those which aredescribed hereinabove. The polymerization of these monomers emulsifiedin water can be carried out using conventional emulsion polymerizationprocedures. Typically such polymerization reactions are carried out inthe presence of one or more anionic, cationic, amphoteric, or nonionicsurfactants. The suitable surfactants are those which are describedhereinabove.

[0169] The monomers, i.e., the monomer I and the copolymerizablemonomers of this invention are polymerized by means of a catalyticamount of a conventional free radical polymerization catalyst orcatalyst system (which can also be referred to as an additionpolymerization catalyst, a vinyl polymerization catalyst, or apolymerization initiator), preferably, one which is substantially watersoluble. Among such catalysts are peroxides, such as hydrogen peroxide,tertiary butyl hydroperoxide, cumene hydroperoxide; alkali metal (e.g.,sodium, potassium, or lithium), and ammonia persulfates, perphosphates,and perborates; azo nitriles, such as α,α-azobisisobutyronitrile, andwater soluble azo initiators, such as WAKO™ initiators; and redox systemincluding such combinations as mixtures of hydrogen peroxide, t-butylhydroperoxide or the like, and any of the iron salts, titanous salts,zinc formaldehyde sulfoxylate, or sodium formaldehyde sulfoxylate;alkali metal or ammonium persulfate, perborate, or perchlorate togetherwith an alkali metal bisulfite, such as sodium metabisulfite; and alkalimetal persulfate together with an aryl phosphinic acid such as benzenephosphinic acid and the like.

[0170] The temperature at which step (b) is conducted ranges from about10° C. to about 90° C., preferably from about 20° C. to about 75° C. Thepressure in this step (b) is not critical and can be subatmospheric,atmospheric, or super atmospheric.

[0171] The reaction times in step (b) will generally range from about 1hour to about 6 hours or longer and sometimes under an inert atmospheresuch as nitrogen.

[0172] Using the procedure of step (b) outlined herein, theethylenically unsaturated ester of a long-chain olefinic monomer Iundergoes polymerization reaction with one or more of copolymerizablemonomers to form the polymers dispersed in water.

[0173] In step (c) of the process of this invention the polymer soformed in step (b) still dispersed in water is further blended with atleast one or more of a metal drier, surfactant, and desired combinationsof the additives to form the waterborne formulations suitable for use incoatings, adhesives or inks applications. For instance, the suitablemetal driers, surfactants, and various additives are those describedhereinabove. The amounts of these components used depend on the intendeduse of the formulation and generally range in amounts as describedhereinabove.

[0174] The blending in step (c) can be carried out in any of themixing/blending devices generally known in the art. The temperature atwhich the blending is conducted is generally around ambient conditions,and ranges from about 10° C. to about 40° C. The reaction times forblending generally range from about 10 minutes to about 60 minutes andsometimes under an inert atmosphere such as nitrogen.

[0175] Thus, in one of the preferred embodiments of this invention aprocess for the preparation of a coating composition using theinternally plasticizing compound IV is also provided. Using the processof this invention described hereinabove the coating composition isprepared in this embodiment utilizing the compound IV. Accordingly, thecompound IV is first prepared employing a corresponding hydroxy fattyacid ester and a substituted or unsubstituted acrylic acid or itsderivatives using appropriate esterification conditions discussedhereinabove. The compound IV is then polymerized with one or more ofcopolymerizable monomers using an emulsion polymerization conditions,and in the final step blended with one or more of driers and otherdesirable additives to form the coating composition.

[0176] In yet another aspect the invention provides novel compoundssuitable as internally plasticizing monomers of this invention forforming the novel latex or emulsion compositions described hereinabove.These monomers are substituted ethylenically unsaturated carboxylic acidesters of long-chain olefinic compounds of the formula Ia:

[0177] Where R₁, R₂, R₃, R₄, R₅, R₇, R₉, R₁₀, R₁₁, a, b, and c are asdefined above. R₈ is selected from the group consisting of —CN,—CONR′R″, and —CH₂NR′R″, —CH₂OH, —CH₂OR, where R, R′, and R″ are asdefined above. The preferred monomers are unsubstituted wherein R₁, R₂,R₃, R₄, R₅, R₆, R₇ are hydrogen and are derived from fatty acidsobtained from semi- or non-drying oils such as castor oil andlesquerella oil. The preferred R₁₀ and R₁₁ groups are also hydrogen, andthe preferred R₉ may be either hydrogen or methyl.

[0178] In still another aspect, the invention provides a process for thepreparation of novel monomers Ia using precursor hydroxy long-chaincompounds. The preparation involves an esterification reaction of asuitable hydroxy long-chain compound with an ethylenically unsaturatedcarboxylic acid or its derivatives VI to form the corresponding esterIa. This esterification reaction is identical to the one described abovein step (a) of the process for making the waterborne formulations ofthis invention.

[0179] In yet an additional aspect the invention provides another classof novel compounds suitable as internally plasticizing monomers of thisinvention for forming the novel latex or emulsion compositions describedhereinabove. These monomers are substituted ethylenically unsaturatedcarboxylic acid esters of long-chain olefinic compounds of the formulaIb:

[0180] Where R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₉, R₁₀, R₁₁, a, a′, b, b′, andc are as defined above. R is selected from the group consisting of:

[0181] phenyl and substituted phenyl;

[0182] tolyl and substituted tolyl;

[0183] benzyl and substituted benzyl;

[0184] alkoxyalkyl group having 1 to 10 carbon atoms;

[0185] hydroxyalkyl group having 1 to 10 carbon atoms;

[0186] acyloxyalkyl group having 1 to 10 carbon atoms;

[0187] a linear or branched alkenyl group having 2 to 10 carbon atoms;

[0188] linear or branched alkyl and fluoroalkyl groups having theformula C_(n)H_(x)F_(y), where n is an integer from 2 to 10, x and y areintegers from 0 to 2n+1, and the sum of x and y is 2n+1; and

[0189] a multifunctional moiety having the structure II or III:

[0190] where R₁₂ and R₁₃ are the same or different and are independentlyselected from the group consisting of:

[0191] a substituted or unsubstituted, saturated or unsaturated fattyacid chain;

[0192] acrylic and substituted acrylic;

[0193] a linear or branched alkyl or alkenyl carboxylic acid moietyhaving 2 to 30 carbon atoms; and

[0194] monoalkyl esters of maleic and fumaric acids, where alkyl groupcontains 1 to 4 carbon atoms

[0195] The preferred monomers are unsubstituted wherein R₁, R₂, R₃, R₄,R₅, R₆, R₇ are hydrogen and are derived from fatty acids obtained fromsemi- or non-drying oils such as castor oil and lesquerella oil. Thepreferred R₁₀ and R₁₁ groups are also hydrogen, and the preferred R₉ maybe either hydrogen or methyl.

[0196] In yet a further aspect the invention provides a process for thepreparation of novel monomers Ib using a precursor hydroxy long-chaincompounds. The preparation involves an esterification reaction of asuitable hydroxy long-chain compound with an ethylenically unsaturatedcaroxylic acid or its derivatives VI to form the corresponding ester Ib.This esterification reaction is identical to the one described above instep (a) of the process for making the waterborne formulations of thisinvention. However, if the starting material Ib contains a hydroxyalkylgroup as a substituent on its ester group, i.e., when R=hydroxyalkylgroup, the esterification may be carried out either using excess of theacid or its derivative VI to form a monomer containing the diester ofethylenically unsaturated acid VI, or the hydroxy group is suitablyprotected to form the monoester as described hereinabove.

[0197] As mentioned hereinabove, the compositions of this invention haveutility in a diverse variety of applications. For instance, thecompositions of this invention can be converted to redispersible latexpowder by physical drying of the latex composition. The compositions ofthis invention can also be used to form solvent-free coatings such asadhesives, including pressure sensitive and contact adhesives, which canbe used either at ambient or elevated temperatures. The inks or coatingsformulations formed from the compositions of this invention may be inthe form of waterborne latex or may be in the form of 100% solids. Asignificant advantage of these compositions is that the coatings, inks,and adhesives formed from these compositions are essentially solvent andVOCs free formulations, thus eliminating environmental pollution yetfeaturing enhanced properties.

[0198] This invention is further illustrated by the following exampleswhich are provided for illustration purposes and in no way limit thescope of the present invention.

EXAMPLES

[0199] (General)

[0200] In the Examples that follow, the following abbreviations areused:

[0201] MECO—Methacrylated castor oil

[0202] ACO—Acrylated castor oil

[0203] MECOME—Methacrylated methyl ricinoleate

[0204] ACOME—Acrylated methyl ricinoleate

[0205] MELO—Methacrylated lesquerella oil

[0206] ALO—Acrylated lesquerella oil

[0207] ALOME—Acrylated methyl lesquerolate

[0208] T_(g)—Glass transition temperature.

[0209] NMR—Nuclear magnetic resonance spectroscopy, usually of eitherproton, ¹H; and/or carbon 13, ¹³C nuclei.

[0210] IR—Infrared spectroscopy.

[0211] DSC—Differential Scanning Calorimetry.

[0212] MFT—Minimum film forming temperature.

[0213] PVC—Pigment volume concentration.

[0214] VOC—Volatile organic content

[0215] General Analytical Techniques Used for the Characterization: Avariety of analytical techniques were used to characterize variousstarting materials and the compositions of this invention which includedthe following:

[0216] NMR: ¹H and ¹³C NMR spectra were recorded on a Bruker AX-200 MHzspectrometer with 5 mm probes at 200 and 50 MHz, respectively.

[0217] DSC: A Mettler DSC-30 was used to determine the T_(g) of thefilms (mid point value). The heating rate was maintained at 10°C./minute, generally, over a temperature range of −50° C. to 100° C. Theflow rate of nitrogen or air is maintained at 20 mL/rnin.

[0218] MFT: MFT of latexes were determined by a MFFT Bar 90 equipmentfrom Byk-Gardner in accordance with ASTM procedure No. D-2354.

[0219] Particle Size Determination: Particle size was measured by aCoulter N4 MD sub-micron particle size analyzer.

[0220] Tensile Strength Measurements: The tensile strength and percentelongation of the films were determined with a 810 Material Test Systemaccording to ASTM D-2370. The specimen were cut to a width of 13 mm, athickness of 0.06-0.12 mm, and a gauge length of 15 mm. In most cases,the data reported represents an average of 8 measurements.

[0221] Measurements of Adhesion and Hardness: The clear latex filmadhesion on differing substrates was measured in accordance with ASTMprocedure No. D-3359. The latex hardness development was monitored inaccordance with ASTM procedure No. D-3363.

[0222] Gel Content and Swelling Index: The extent of film cure wasdetermined following the method described in U.S. Pat. No. 4,906,684with minor modifications. The films that were air-dried for two weeks,and removed from the substrate were tested as follows: (1) About 2 gramssamples of films were weighed into glass bottles containing 75 mL oftoluene, the bottles were capped and shaken constantly; (2) after 3days, the bottle contents were decanted onto a weighed fluorocarbon meshscreen (70 micron meter mesh opening), and washed with toluene; (3) themesh screen was weighed, then dried in a vacuum oven until constantweight was obtained; and (4) after determining the weight of wet gel anddry gel, the gel content and swelling index were determined according tothe following equations:

[0223] % Gel Content=(weight of dry gel×100)/weight of film

[0224] Swelling Index=(weight of wet gel−weight of dry gel)/weight ofdry gel

[0225] Dry time: The dry time measurements of the film samples of thecoatings compositions were measured in accordance with ASTM procedureNo. D-1640.

[0226] Conical mandrel (⅛″) measurements on the film samples were madeaccording to ASTM D-522.

[0227] Scrub test was performed in accordance with ASTM procedure No.D-2486.

[0228] Sheen and Gloss of the film samples were measured according toASTM D-523.

[0229] Contrast ratio was measured according to D-3022.

Example A

[0230] Castor oil was transesterified to methyl ricinoleate using thefollowing procedure: 200 grams of castor oil was refluxed with 300 gramsof methanol and 12 grams of sodium methoxide for 1 hour. After removingthe solvent in vacuo, the product was extracted using petroleum ether.Upon drying and complete removal of the residual solvent, methylricinoleate was formed in quantitative yields.

Example B

[0231] Example A was substantially repeated in Example B with theexception that the reaction was carried out using lesquerella oilinstead of castor oil as follows. 1000 grams of lesquerella oil wasrefluxed with 1500 grams of methanol and 60 grams of sodium methoxidefor 3 hours. After removing the solvent in vacuo, the product wasextracted using petroleum ether. The product was dried and the solventwas removed. Methyl lesquerolate was present in 53-60% mixed with othermethyl esters of fatty acids. Purification of methyl lesquerolate fromthe mixture of methyl esters of fatty acids was performed by vacuumdistillation. Several nonhydroxy fractions were distilled at differenttimes in the beginning and the residue in the distillation flask waschecked using GC-mass spectroscopy. When the residue contained higherthan 93% pure methyl lesquerolate, the distillation was stopped and theproduct isolated (yield, 550 grams).

Example 1

[0232] Castor oil (207 g; 0.627 hydroxy equivalent) was placed in athree-neck flask under a blanket of nitrogen. The entire reactioncontents were cooled in an ice bath. Methacryloyl chloride (25.6 g;0.246 mol equivalent) dissolved in 75 mL of methylene chloride was addedslowly to the cooled castor oil with vigorous stirring in about 2 hours.Triethylamine (22.5 g; 0.223 mol equivalent) dissolved in 50 mL ofmethylene chloride was subsequently added in about an hour. Afteraddition of triethylamine, the solution was allowed to warm to ambienttemperature and was stirred for another 4 hours in order to complete thereaction. The precipitated triethylammonium chloride was removed byfiltration, and the filtrate was washed with brine solution (saturatedNaCI) followed by washings with dil. NaOH and dil. HCI. The organiclayer was dried with anhydrous magnesium sulfate and the solvent wasremoved in vacuo to yield methacrylated castor oil (MECO) in essentiallyquantitative yields. MECO was stabilized from polymerization by additionof approximately 10 ppm hydroquinone. The structure of the product wasverified by ¹H and ¹³C NMR spectroscopy.

Example 2

[0233] Example 1 was substantially repeated in Example 2 with theexception that the reaction was carried out using acryloyl chloride andcastor oil as follows. About 500 grams of castor oil (1.52 mol hydroxyequivalent) was reacted with 149 grams (1.65 mol equivalent) of acryloylchloride in the presence of 223 grams of triethylamine (2.21 molequivalent). The reaction was performed using 500 mL of benzene as asolvent. Yield of acrylated castor oil (ACO) was 462 grams. The productwas characterized by ¹H and ¹³C NMR spectroscopy.

Example 3

[0234] Example 1 was substantially repeated in Example 3 with theexception that the reaction was carried out using methacryloyl chlorideand methyl ricinoleate as follows. About 103 grams of methyl ricinoleate(0.312 mol hydroxy equivalent) was reacted with 37 grams (0.356 molequivalent) of methacryloyl chloride in the presence of 60 grams oftriethylamine (0.594 mol equivalent). The reaction was performed using200 mL of methylene chloride as a solvent. A quantitative yield ofmethacrylated methyl ricinoleate (MECOME) was obtained and wascharacterized by ¹H and ¹³C NMR techniques.

Example 4

[0235] Example 1 was substantially repeated in Example 4 with theexception that the reaction was carried out using acryloyl chloride andmethyl ricinoleate as follows. About 140 grams of methyl ricinoleate(0.424 mol hydroxy equivalent) was reacted with 37 grams (0.36 molequivalent) of acryloyl chloride in the presence of 60 grams oftriethylamine (0.59 mol equivalent). The reaction was performed using200 mL of methylene chloride as a solvent. A quantitative yield ofacrylated methyl ricinoleate (ACOME) was obtained and was characterizedby ¹H and ¹³C NMR techniques.

Example 5

[0236] Example 1 was substantially repeated in Example 5 with theexception that the reaction was carried out using methacryloyl chlorideand lesquerella oil as follows. About 220 grams of lesquerella oil(0.430 mol hydroxy equivalent) was reacted with 24.0 grams (0.230 molequivalent) of methacryloyl chloride in the presence of 24.2 grams oftriethylamine (0.239 mol equivalent) and using 300 mL of methylenechloride as a solvent. A quantitative yield of methacrylated lesquerellaoil (MELO) was obtained and was characterized by ¹H and ¹³C NMRtechniques.

Example 6

[0237] Example 1 was substantially repeated in Example 6 with theexception that the reaction was carried out using acryloyl chloride andlesquerella oil as follows. About 500 grams of lesquerella oil (0.980mol hydroxy equivalent) was reacted with 97.6 grams (0.1.08 molequivalent) of acryloyl chloride in the presence of 149 grams oftriethylamine (1.48 mol equivalent) and 500 mL of benzene as a solvent.Acrylated lesquerella oil (yield: 519 grams) (ALO) was characterized by¹H and ¹³C NMR techniques.

Example 7

[0238] Example 1 was substantially repeated in Example 7 with theexception that the reaction was carried out using acryloyl chloride andmethyl lesquerolate as follows. About 335 grams of methyl lesquerolate(0.900 mol hydroxy equivalent) was reacted with 93.3 grams (83.8 molequivalent) of acryloyl chloride in the presence of 136.6 grams oftriethylamine (1.35 mol equivalent) and 1200 mL of benzene as a solvent.Acrylated methyl lesquerolate(ALOME) (yield, 375.2 grams) wascharacterized by ¹H and ¹³C NMR techniques.

Example 8

[0239] This Example 8 illustrates the preparation of a latex containingthe internally plasticizing long-chain olefinic monomer of thisinvention. To a 1 L reactor kettle equipped with an impeller and chargedwith 110 grams of deionized (DI) water, which had been deoxygenated (DO)for about half an hour by heating to 80° C. under a nitrogen atmosphere,was added polyvinyl alcohol (80 grams of 10% solution) followed by theaddition of 12 grams of Igepal CA-897 (octylphenol ethoxylates with 40moles of ethylene oxide units obtained from Rhone-Poulenc), 1.2 grams ofIgepal CA-630 (octylphenol ethoxylates with 9 moles of ethylene oxideunits obtained from Rhone-Poulenc), and 0.6 grams of sodium bicarbonate.The contents were maintained at 80° C. under a blanket of nitrogen, andthe preseeding was affected by the addition of ammonium persulfate (0.6grams) and vinyl acetate (40 grams), and increasing the impeller speedto 200 rpm.

[0240] After 15 minutes of preseeding a monomer mixture or pre-emulsion(a stable pre-emulsion can be obtained by mixing all the desirablemonomers, surfactants and water over a stir plate for few minutes)consisting of 30 grams of MECOME (from Example 3) and 130 grams of vinylacetate was added over a period of 3.5 hours at 75° C. maintaining theimpeller speed at 200 rpm. Additional amounts of ammonium persulfate(0.6 grams) dissolved in 30 grams of DI water was cofed into the reactorover a period of 3.75 hours. After the addition of all of the monomersand initiators, the contents of the reactor were stirred at 150 rpm foran additional period of 2 hours at 80° C. The cooled latex was filteredfrom a cheese cloth or a medium mesh filter and poured into a cleancontainer for further evaluation.

[0241] The latex exhibited the following properties: particle size: 190nm; MFT: −1° C.; pH: 4.6; solid contents: 48%; and T_(g): 18.4° C. (withno driers added). The film formed from the latex exhibited the followingfilm properties: gel content: 62%; swelling: 20; tensile strength: 330psi; and elongation: 1260%.

Example 9-10

[0242] Example 8 was substantially repeated in Examples 9 and 10 withthe exception that the latex was prepared using the following amounts ofmaterials in each of these examples: Example 9 Example 10^(c) 10%Polyvinyl alcohol 40 grams 60 grams Igepal CA-897 (Rhone Poulenc) 12grams 12 grams Igepal CA-630 (Rhone Poulenc) 1.2 grams 1.2 grams NaHCO₃0.8 grams 0.8 grams DI, DO water 150 grams 140 grams Ammonium persulfate0.6 grams 0.2 grams Vinyl acetate - for seeding 40 grams — Vinylacetate - with monomer emulsion 114 grams 147 grams MECO^(a) — 16 gramsACOME^(b) 16 grams — Butyl acrylate 30 grams 34 grams Sipomer WAM II(Rhone Poulenc) — 3 grams Ammonium persulfate - initiator feed 0.6 grams0.8 grams DI, DO water - for initiator feed 30 grams 30 grams

[0243] In both examples, the seeding was done at 80° C. for about 10minutes, and the polymerization itself was conducted at 72° C. Themonomers were added during a period of about 3.5 hours at an impellerspeed of 200 rpm, along with the initiator cofed for about 3.75 hours,and post polymerized for about 1.5 hours. The latices and the filmsformed from them exhibited the following properties: Example 9 Example10 Particle Size 180 nm 190 nm MFT −1° C. 2° C. pH 4.9 5.1 Solid content45% 43% T_(g) 17 22 % Gel Content - of film 61 54 Swelling - of film 2418 Tensile strength - of film — 860 psi Tensile elongation - of film —1060%

Examples 11-13

[0244] These examples illustrate the effect of metal driers on the filmsafter curing. Example 8 was substantially repeated in Examples 11 to 13with the exception that the latex was prepared using the followingamounts of materials in each of these examples: Example 11 Example 12Example 13 10% Polyvinyl alcohol 81 grams — — Igepal CA-897 (RhonePoulenc) 12.3 grams — — Sodium dodecylbenzene sulfonate — — 0.5 gramsAbex 40^(a) — 3.5 grams — Rhodofac BX-660^(b) (Rhone Poulenc) — 3.5grams — Sipomer BEM^(c) (Rhone Poulenc) — 1.2 grams — NaHCO₃ 0.6 grams0.6 grams — DI, DO water 100 grams 140 grams 50 grams Ammoniumpersulfate 0.6 grams 0.2 grams 0.1 grams Vinyl acetate - for seeding 40grams 10 grams — Preemulsion monomer mixture: Vinyl acetate - withmonomer emulsion 107 grams 56 grams 70 grams Internally plasticizingmonomer ALO^(d) ALO^(d) ALOME^(e) 50 grams 8 grams 7 grams Butylacrylate 34 grams 25 grams 11.5 grams Veova 10 (Shell) — — 10 gramsSipomer WAM I (Rhone Poulenc) 1.5 grams 0.75 grams 0.6 grams Sipomer WAMII (Rhone Poulenc) 1.5 grams 0.75 grams 0.7 grams Ammonium persulfate -initiator feed 0.6 grams 0.4 grams 0.4 grams Sodium dodecylbenzenesulfonate — — 0.5 grams Igepal CA897 (Rhone Poulenc) — — 3.5 gramsSodium carbonate — — 0.4 grams DI, DO water - for initiator feed 30grams 12 grams 60 grams Chaser Solution FeSO₄ — — 0.01 grams t-Butylhydroperoxide — — 0.4 grams Sodium formaldehyde sulfoxylate — — 0.3grams DI water — — 8.5 grams

[0245] In all of these examples, the seeding was done at 80° C. forabout 10 to 15 minutes, and the polymerization itself was conducted at72° C. The monomers were added during a period of about 3.5 hours (inabout 2 hours in Example 13) at an impeller speed of 200 rpm, along withinitiator cofed for about 3.75 hours in Example 11, 1.5 hours in Example12, and 2.5 hours in Example 13; and post polymerized for about 2 hoursin Examples 11 and 13, and 0.75 hours in Example 12.

[0246] The films were formed in these examples with and without theaddition of metal driers. The samples with metal driers contained 0.08weight percent (based on solids) of cobalt hydro-cure II (obtained fromOMG, Inc., Cleveland, Ohio) as a metal drier, 0.5 weight percent (basedon solids) DRI-RX (obtained from OMG, Inc., Cleveland, Ohio) as a drieraccelerator, and 1 weight percent methyl ethyl ketone peroxide as a freeradical initiator. The latices and the films formed from them exhibitedthe following properties: Example 11 Example 12 Example 13 Particle Size200 nm 200 nm 180 nm MFT 0° C. 1° C. 0° C. pH 4.9 4.9 4.8 Solid content48% 42% 50% T_(g) (with no driers added) 20 19 29 T_(g) (after theaddition of 39 27 48* driers)

Examples 14-15

[0247] Example 8 was substantially repeated in Examples 14 and 15 withthe exception that the latex was prepared using the following amounts ofmaterials in each of these examples: Example 14 Example 15 10% Polyvinylalcohol 20 grams — Igepal CA-897 (Rhone 6.3 grams — Poulenc) IgepalCA-630 (Rhone 1.2 grams — Poulenc) Abex 3384 (40% solids) — 3 gramsRhodofac 13X660 (80% — 3 grams solids) (Rhone Poulenc) Sipomer cops-I(40% solids)^(a) — 18 grams (Rhone Poulenc) Na₂CO₃ 0.4 grams 1 grams DI,DO water 100 grams 120 grams Ammonium persulfate 0.1 grams 0.05 gramsPreemulsion monomer mixture: Styrene - preemulsion 47 grams — additionInternally plasticizing ACOME^(b) ACOME^(b) monomer 10 grams 8 gramsMethyl methacrylate — 40 grams Butyl acrylate 42 grams 50 grams Acrylicacid — 1.5 grams Sipomer WAM I (Rhone 0.75 grams 0.75 grams Poulenc)Sipomer WAM II (Rhone 0.75 grams 0.75 grams Poulenc) Igepal CA897 (Rhone8 grams — Poulenc) Sipomer cops (Rhone — 18 grams Poulenc) Ammoniumpersulfate - 0.4 grams 0.4 grams initiator feed DI, DO water - for 27grams 7 grams initiator feed Chaser solution FeSO₄ — 0.01 grams t-Butylhydroperoxide 0.4 grams 0.1 grams Sodium formaldehyde 0.4 grams 0.3grams sulfoxylate DI water 9 grams 9 grams

[0248] In both of these examples, the seeding was done at 60° C. forabout 10 to 15 minutes, and the polymerization itself was conducted at60° C. The monomers were added during a period of about 2 hours at animpeller speed of 200 rpm, along with the initiator cofed for about 2.5hours, and post polymerized for about 1.5 to 2 hours at 80° C. Thelatices and the films formed from them exhibited the followingproperties: Example 14 Example 15 Particle Size 160 nm 140 nm MFT −1° C.−4° C. pH 4.9 4.3 Solid content 40% 52% T_(g) (with no driers added) 13— T_(g) (after the addition of drier) 48* 49*

Examples 16 and 17

[0249] Examples 16 and 17, illustrate the formation of the Mill Baseformulations used for the preparation of coatings compositions.Specified amounts of the ingredients given below were added to aLightnin mixer at a mixing speed of 800 rpm, and mixed further at 3500rpm for 20 minutes. Ingredients Example 16 Example 17 Tronox CR-800(Kerr McGee) 455 grams 1200 grams Huber 70C (DuPont) 292.5 grams —Beaverwhite 325 (ECC) 260 grams — Duramite (ECC) 325 grams — NatrosolPlus (Aqualon) 12 grams 5 grams Kathon LX 1.5% (Rohm & Haas) 5 grams 4grams KTPP (Aldrich) 6.5 grams 5 grams Byk 034 (Byk Chemie) 12 grams 9grams Tamol 731 25% (Rohm & Haas) 39 grams 30 grams Surfynol 465 (AirProducts) — 4 grams DI water 715 grams 500 grams

Examples 18 and 19

[0250] The Examples 18 and 19 illustrate the formation of coatingscompositions using the polymeric latices of this invention. The laticesformed in Examples 9 and 10 were used in these Examples to form thevinyl-acrylic latex coatings compositions. The coatings were pigmentedat 55% pigment volume concentration PVC) using the Mill Base formulationof Example 16. The ingredients and the respective amounts for formingthe coatings compositions are given below. For comparison, a controlexperiment, “Control A,” was also carried out using a commercialvinyl-acrylic latex, which had the following properties: MFT: 10° C.;T_(g): 18° C.; and particle size: 330 nm. The following coatingscompositions were prepared using a Lightnin mixer set at 200 rpm.Ingredients Example 18 Example 19 Control A Example 16 - 180 grams 180grams 180 grams Mill Base Formulation DI water 30 grams 22 grams 36grams Na₂CO₃ (20%) 6 grams 7 grams 6 grams Byk 035 (Byk 0.4 grams 0.4grams 0.4 grams Chemie) Surfynol 465 (Air 1 gram 1 gram 1 gram Products)Latex Example 9 Example 10 Commercial % solids 45 43 55 Amount 87 grams92 grams 71 grams Rompaque OP - 62 LO 20 grams 20 grams 20 grams (36.5%)(Rohm & Haas) Polyphobe 107 (25%) 0.8 grams 1.2 grams 1.3 grams (UnionCarbide) Polyphobe 102 (25%) 5 grams 6 grams 6.4 grams (Union Carbide)Butyl cabitol — — 3 grams Propylene glycol — — 7 grams

[0251] The coatings of Example 18, 19, and the Control A exhibited thefollowing properties: Coating Properties Example 18 Example 19 Control APVC 55% 55% 55% Volume Solids 33.6% 33% 33.5% Weight Solids 49.9% 50%49.6% Stormer Viscosity 99 KU 100 KU 105 KU ICI Viscosity 1.6 poise 2poise 2 poise pH 9.1 9.4 8.6 VOC (grams/Liter) <0.4 <0.4 122

[0252] Coating films were cast onto Leneta charts, aluminum and steelpanels. The dry time for the solventless latex coatings was less thanthe control, their respective films are significantly harder than thosefrom the Control A or other commercial coatings requireing coalescingaids, and adhesion of the solventless coatings of Examples 18 and 19were superior to the coalescent containing Control A. The MFTs of thesolventless coatings of Example 18 and 19 were similar to thoseformulated with the assistance of organic coalescing aids. Comparativeproperties of the films formed from the coating compositions of Examples18 and 19, and the Control A are given below. Film Properties Example 18Example 19 Control A Tensile strength 853 psi 884 psi 596 psi Elongationat 8.4% 8.6% 26% break Wet thickness 7 mil 7 mil 7 mil Volume solids33.6% 33% 33.5% Dry time 50 minutes 40 minutes 55 minutes MFT 0° C. 0°C. 1° C. Pencil hardness 4 H 4 H 2 H Conical mandrel pass pass pass (⅛″)Adhesion on Al 100% 100% 80% Adhesion on steel 100% 100% 80% Scrub test:Initial 170 160 170 break Scrub test: Film 240 230 250 failure Sheen,85° 1.9 1.9 1.7 Contrast ratio 95 95 94

[0253] Various other coatings compositions at different levels of PVC orsolid contents of the latices can be made using the procedures ofExamples 18 and 19.

Examples 20 and 21

[0254] The Examples 20 and 21 illustrate the formation of solventlesscoatings compositions containing the styrene-acrylic (Example 14) andall-acrylic latex polymers (Example 15). Examples 18 and 19 weresubstantially repeated in Examples 20 and 21 with the exception that theMill Base formulation of Example 17 was used with the latices ofExamples 14 and 15. For comparison, two control compositions, Control Band Control C, were also prepared under similar conditions usingcommercial styrene-acrylic (MFT: 1° C., particle size: 80 nm, and T_(g):−2° C.) and all-acrylic (MFT: 9° C., particle size: 500 nm, and T_(g):14° C.) latices. Specific amounts of the ingredients used for formingthe coatings formulations in Examples 20 and 21, and the respectivecontrols are given below: Example Example Ingredients 20 Control B 21Control A Example 17 - 100 100 100 100 Mill Base grams grams grams gramsFormulation DI water 35 60 35 60 grams grams grams grams Na₂CO₃ (20%)8.4 8 8.4 8 grams grams grams grams Byk 035 (Byk 0.4 0.4 0.4 0.4 Chemie)grams grams grams grams Surfynol 465 (Air 1.6 1.6 1.6 1.6 Products)gram  gram  gram  grams Latex Example Commercial Example Commercial 1415 % solids - 45 55 45 55 Amount 170 138 170 138 grams grams grams gramsPolyphobe 107 1 1.3 1 1.3 (25%) (Union grams grams grams grams Carbide)Polyphobe 102 7 11 7 11 (25%) (Union grams grams grams grams Carbide)Butyl cabitol — 3 — 3 grams grams Propylene glycol — 7 — 7 grams grams

[0255] The coatings of Examples 20, 21, and the Controls B and Cexhibited the following properties: Coating Properties Example 20Control B Example 21 Control C PVC 20%   20% 20%   20% Volume Solids 33%32.6% 33% 32.6% Weight Solids 46.3%   45.6% 46.3%   45.6% Stormerviscosity 82 KU 84 KU 82 KU 84 KU ICI 1.2 poise 1.2 poise 1.2 poise 1.2poise pH 8.2 9.1 8.2 9.1 VOC (grams/Liter) <0.43 118 <0.43 118

[0256] The coating films were formed and tested from Examples 20, 21,and the Controls B and C following the procedures of Examples 18 and 19.Comparative properties of the films formed from the coating compositionsof Examples 20, 21, and the Controls B and C are given below. ExampleExample Film Properties 20 Control B 21 Control C Wet thickness 6 mil 6mil 6 mil — Dry time 50 70 55 60 minutes minutes minutes minutes MFT −2°C. −4° C. −2° C. 6° C. Pencil hardness F 2B F B Conical mandrel (⅛″)pass pass pass pass Adhesion on Al 80% 80% 100% 80% Adhesion on steel80% 80% 100% 80% Gloss, 85 89 93 83 82 Gloss, 60 72 75 64 65 Gloss, 20°26 32 20 19 Contrast ratio 97.3 97.2 97.5 97

Example 22

[0257] This Example 22 illustrates the use of the internallyplasticizing monomer of this invention directly in an UV curableformulation. An ink formulation was made using the monomer compositionof Example 7, ALOME as follows. Specified amounts of the ingredients asgiven below were blended in a Lightnin mixer at 150 rpm for one hour andthen to insure thorough mixing the ingredients were transferred to aball mill and ground to a Hegman #7. Ingredients Parts by weight ALOME,from Example 7 21.4 Fluorescent rocket red AX-135 (Day Glo Color) 1.0Photomer 3016 (Henkel) 17.0 Photomer 4061 (Henkel) 19.0 Photomer 4094(Henkel) 15.6 Photomer 4149 (Henkel) 4.4 Photomer 4770 (Henkel) 5.5Photomer 6008 (Henkel) 11.2 Byk 065 (Byk Chemie) 0.4 Byk 358 (BykChemie) 0.3 Byk 325 (Byk Chemie) 0.3 Irgacure 651 (Ciba) 2.7Benzophenone 1.3

[0258] A 2 mil thick film was applied onto wood, aluminum, paper andsteel panels with a draw bar, and irradiated under a 600 W mediumpressure mercury UV lamp for 4 seconds at a distance of approximately 7″with a Fusion UV curing source to a hard, smooth film. Similarformulations and applications can be developed using other specialtymonomers described herein.

[0259] Although the invention has been illustrated by certain of thepreceding examples, it is not to be construed as being limited thereby;but rather, the invention encompasses the generic area as hereinbeforedisclosed. Various modifications and embodiments can be made withoutdeparting from the spirit and scope thereof

What is claimed is:
 1. A substituted ethylenically unsaturatedcarboxylic acid ester of a long-chain olefinic compound of the formula:

wherein (a) R₁, R₂, R₃, R₄, R₅, R₆, and R₇, are the same or differentand are each independently selected from the group consisting of:hydrogen; alkoxy group having 1 to 10 carbon atoms; alkoxyakl grouphaving 1 to 10 carbon atoms; and linear or branched alkyl andfluoroalkyl groups having the formula C_(n)H_(x)F_(y), where n is aninteger from 1 to 10, x and y are integers from 0 to 2n+1, and the sumof x and y is 2n+1; (b) R₈ is selected from the group consisting of:—CN; —CH₂OH; —CH₂OR; —CONR′R″; and —CH₂NR′R″; where R, R′, and R″ arethe same or different and are independently selected from the groupconsisting of: hydrogen; phenyl and substituted phenyl; tolyl andsubstituted tolyl; benzyl and substituted benzyl; alkoxyalkyl grouphaving 1 to 10 carbon atoms; hydroxyalkyl group having 1 to 10 carbonatoms; acyloxyalkyl group having 1 to 10 carbon atoms; a linear orbranched alkenyl group having 2 to 10 carbon atoms; and linear orbranched alkyl and fluoroalkyl groups having the formulaC_(n)H_(x)F_(y), where n is an integer from 1 to 10, x and y areintegers from 0 to 2n+1, and the sum of x and y is 2n+1; (c) R₉, R₁₀,and R₁₁ are the same or different and are independently selected fromthe group consisting of: hydrogen; a carboxylate of the formula —COOR,where R is alkyl group having 1 to 10 carbon atoms, or phenyl andsubstituted phenyl; phenyl and substituted phenyl; tolyl and substitutedtolyl; benzyl and substituted benzyl; a linear or branched alkenyl grouphaving 2 to 10 carbon atoms; and linear or branched alkyl andfluoroalkyl groups having the formula C_(n)H_(x)F_(y), where n is aninteger from 1 to 10, x and y are integers from 0 to 2n+1, and the sumof x and y is 2n+1; and (d) a, a′, b, b′, and c, are integers, where aand a′ have a value of from 0 to 10, b and b′ have a value of 0 to 2with the proviso that sum of b and b′ is 1 or 2, and c has a value offrom 0 to
 20. 2. The compound as set forth in claim 1 wherein it isderived from a hydroxy fatty acid selected from the group consisting ofricinoleic, lesquerolic, auricolic, and densipolic acid.
 3. The compoundas set forth in claim 1 wherein it is derived from a non-drying oilselected from the group consisting of castor oil and lesquerella oil. 4.The compound as set forth in claim 3 wherein R₁₀ and R₁₁ are hydrogen,and R₉ is either methyl or hydrogen.
 5. The compound as set forth inclaim 1 wherein said ethylenically unsaturated carboxylic acid ester ofa long-chain compound is derived from a carboxylic acid selected fromthe group consisting of acrylic, methacrylic, maleic, fumaric, itaconic,ethacrylic, crotonic, citraconic, cinnamic, methyl hydrogen fumarate,benzyl hydrogen maleate, butyl hydrogen maleate, octyl hydrogenitaconate, and dodecyl hydrogen citraconate.
 6. A compound suitable forforming latex or emulsion coatings comprising a derivative of anon-drying oil having a substituted ethylenically unsaturated carboxylicacid ester of a long-chain olefinic moiety of the formula:

wherein (a) R₈ is selected from the group consisting of: —CN; —CH₂OH;—CH₂OR; —CONR′R″; and —CH₂NR′R″; where R, R′, and R″ are the same ordifferent and are independently selected from the group consisting of:hydrogen; phenyl and substituted phenyl; tolyl and substituted tolyl;benzyl and substituted benzyl; alkoxyalkyl group having 1 to 10 carbonatoms; hydroxyalkyl group having 1 to 10 carbon atoms; acyloxyalkylgroup having 1 to 10 carbon atoms; a linear or branched alkenyl grouphaving 2 to 10 carbon atoms; and linear or branched alkyl andfluoroalkyl groups having the formula C_(n)H_(x)F_(y), where n is aninteger from 1 to 10, x and y are integers from 0 to 2n+1, and the sumof x and y is 2n+1; (b) R₉ is either hydrogen or methyl; and (c) a, a′,b, b′, and c are integers, where a and a′ have a value of from 2 to 4, band b′ have a value of 0 to 2 with the proviso that sum of b and b′ is 1or 2, and c has a value of 5 to
 12. 7. The compound as set forth inclaim 6 wherein said long-chain olefinic moiety is derived from eithercastor oil or lesquerella oil.
 8. A coating formulation comprising acompound as set forth in claim 6 .
 9. An adhesive formulation comprisinga compound as set forth in claim 6 .
 10. An ink formulation comprising acompound as set forth in claim 6 .
 11. A process for preparingethylenically unsaturated esters of long-chain olefinic compoundsderived from a semi- or non-drying oil comprising the step of subjectinga substituted long-chain olefinic compound having a hydroxy group tosuitable esterification conditions in the presence of an ethylenicallyunsaturated carboxylic acid or its suitable derivative for a sufficientperiod of time and under suitable conditions of temperature and pressureto form the corresponding ethylenically unsaturated ester of along-chain olefinic compound.
 12. The process as set forth in claim 11wherein said substituted long-chain olefinic compound has the formula:

wherein (a) R₁, R₂, R₃, R₄, R₅, R₆, and R₇, are the same or differentand are each independently selected from the group consisting of:hydrogen; alkoxy group having 1 to 10 carbon atoms; alkoxyalkyl grouphaving 1 to 10 carbon atoms; and linear or branched alkyl andfluoroalkyl groups having the formula C_(n)H_(x)F_(y), where n is aninteger from 1 to 10, x and y are integers from 0 to 2n+1, and the sumof x and y is 2n+1; (b) R₈ is selected from the group consisting of;—CN; —CH₂OH; —CH₂OR; —CONR′R″; and —CH₂NR′R″, where R, R′, and R″ arethe same or different and are independently selected from the groupconsisting of: hydrogen; phenyl and substituted phenyl; tolyl andsubstituted tolyl; benzyl and substituted benzyl; alkoxyalkyl grouphaving 1 to 10 carbon atoms; hydroxyalkyl group having 1 to 10 carbonatoms; acyloxyalkyl group having 1 to 10 carbon atoms; a linear orbranched alkenyl group having 2 to 10 carbon atoms; and linear orbranched alkyl and fluoroalkyl groups having the formulaC_(n)H_(x)F_(y), where n is an integer from 1 to 10, x and y areintegers from 0 to 2n+1, and the sum of x and y is 2n+1; and (c) a, a′,b, b′, and c, are integers, where a and a′ have a value of from 0 to 10,b and b′ have a value of 0 to 2 with the proviso that sum of b and b′ is1 or 2, and c has a value of from 0 to
 20. 13. The process as set forthin claim 12 wherein said long-chain olefinic compound is derived from ahydroxy fatty acid selected from the group consisting of ricinoleic,lesquerolic, auricolic, and densipolic acid.
 14. The process as setforth in claim 12 wherein said long-chain olefinic compound is derivedfrom a non-drying oil selected from the group consisting of castor oiland lesquerella oil.
 15. The process as set forth in claim 11 whereinsaid ethylenically unsaturated carboxylic acid or its derivatives hasthe formula:

wherein (a) R₉, R₁₀, and R₁₁ are the same or different and areindependently selected from the group consisting of: hydrogen; acarboxylate of the formula —COOR, where R is alkyl group having 1 to 10carbon atoms, or phenyl and substituted phenyl; phenyl and substitutedphenyl; tolyl and substituted tolyl; benzyl and substituted benzyl; alinear or branched alkenyl group having 2 to 10 carbon atoms; and linearor branched alkyl and fluoroalkyl groups having the formulaC_(n)H_(x)F_(y), where n is an integer from 1 to 10, x and y areintegers from 0 to 2n+1, and the sum of x and y is 2n+1; and (b) X isselected from the group consisting of: Br; Cl; hydroxy; alkoxy grouphaving 1 to 4 carbon atoms; and acyloxy group either derived from saidethylenically unsaturated carboxylic acid or having 2 to 4 carbon atoms.16. The process as set forth in claim 11 wherein said ethylenicallyunsaturated ester of a long-chain olefinic compound has the formula:

wherein (a) R₁, R₂, R₃, R₄, R₅, R₆, and R₇, are the same or differentand are each independently selected from the group consisting of:hydrogen; alkoxy group having 1 to 10 carbon atoms; alkoxyalkyl grouphaving 1 to 10 carbon atoms; and linear or branched alkyl andfluoroalkyl groups having the formula C_(n)H_(x)F_(y), where n is aninteger from 1 to 10, x and y are integers from 0 to 2n+1, and the sumof x and y is 2n+1; (b) R₈ is selected from the group consisting of;—CN; —CH₂OH; —CH₂OR; —CONR′R″; and —CH₂NR′R″; where R, R′, and R″ arethe same or different and are independently selected from the groupconsisting of: hydrogen; phenyl and substituted phenyl; tolyl andsubstituted tolyl; benzyl and substituted benzyl; alkoxyalkyl grouphaving 1 to 10 carbon atoms; hydroxyalkyl group having 1 to 10 carbonatoms; acyloxyalkyl group having 1 to 10 carbon atoms; a linear orbranched alkenyl group having 2 to 10 carbon atoms; and linear orbranched alkyl and fluoroalkyl groups having the formulaC_(n)H_(x)F_(y), where n is an integer from 1 to 10, x and y areintegers from 0 to 2n+1; (c) R₉, R₁₀, and R₁₁ are the same or differentand are independently selected from the group consisting of: hydrogen; acarboxylate of the formula —COOR, where R is alkyl group having 1 to 10carbon atoms, or phenyl and substituted phenyl; phenyl and substitutedphenyl; tolyl and substituted tolyl; benzyl and substituted benzyl; alinear or branched alkenyl group having 2 to 10 carbon atoms; and linearor branched alkyl and fluoroalkyl groups having the formulaC_(n)H_(x)F_(y), where n is an integer from 1 to 10, x and y areintegers from 0 to 2n+1, and the sum of x and y is 2n+1; and (d) a, a′,b, b′, and c, are integers, where a and a′ have a value of from 0 to 10,b and b′ have a value of 0 to 2 with the proviso that sum of b and b′ is1 or 2, and c has a value of from 0 to
 20. 17. The process as set forthin claim 11 wherein the temperature is from about −10° C. to about 150°C. and the pressure is atmospheric.
 18. A product produced in accordancewith the process of claim 11 .
 19. A process for preparing a coatingcomposition containing acrylate or methacrylate ester of a hydroxylong-chain compound which comprises the steps of: (a) subjecting ahydroxy fatty compound of the formula:

to esterification conditions in the presence of a substituted acrylicacid or its derivatives of the formula:

at a temperature of about 10° C. to about 100° C. for a period of about15 minutes to about 6 hours to form the corresponding acrylate ester ofthe hydroxy fatty compound of the formula:

(b) subjecting said acrylate ester of hydroxy fatty compound to emulsionpolymerization conditions in an aqueous phase in the presence ofpolymerizable comonomers selected from the group consisting of vinylacetate, vinyl chloride, vinyl ester of versatic acid, acrylic acid,acrylonitrile, acrylamide, butyl acrylate, butyl methacrylate, methylacrylate, methyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexylmethacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate,glycidyl acrylate, glycidyl methacrylate, and styrene; and a suitablefree radical initiator at a temperature of about 20° C. to about 75° C.for a period of about 1 hour to 6 hours to form a polymer of saidacrylate ester of hydroxy fatty compound with said comonomers; and (c)blending said polymer with at least one metal drier selected from thegroup consisting of aliphatic or aromatic carboxylic acid salts ofcobalt, manganese, lead, zirconium, calcium, and mixtures thereof, andin the presence of at least one ionic or non-ionic surface-active agentto form the latex; wherein (i) R₈ is selected from the group consistingof: —CN; —CH₂OH; —CH₂OR; —CONR′R″; and —CH₂NR′R″; where R, R′, and R″are the same or different and are independently selected from the groupconsisting of: hydrogen; phenyl and substituted phenyl; tolyl andsubstituted tolyl; benzyl and substituted benzyl; hydroxyalkyl grouphaving 1 to 10 carbon atoms; alkoxyalkyl group having 1 to 10 carbonatoms; acyloxyalkyl group having 1 to 10 carbon atoms; a linear orbranched alkenyl group having 2 to 10 carbon atoms; and linear orbranched alkyl and fluoroalkyl groups having the formulaC_(n)H_(x)F_(y), where n is an integer from 1 to 10, x and y areintegers from 0 to 2n+1; (b) R₉ is either hydrogen or methyl; (c) X isselected from the group consisting of: Br; Cl; hydroxy; alkoxy grouphaving 1 to 4 carbon atoms; and acyloxy group either derived from saidethylenically unsaturated carboxylic acid or having 2 to 4 carbon atoms;and (d) a, a′, b, b′, and c are integers, where a and a′ have a value offrom 2 to 4, b and b′ have a value of 0 to 2 with the proviso that sumof b and b′ is 1 or 2, and c has a value of 5 to
 12. 20. A productproduced in accordance with the process of claim 19 .